JP3377435B2 - Copper complex catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The invention of the present application relates to a copper complex catalyst for oxygen reduction, which is useful for reducing dissolved oxygen in water and an organic solvent and can also be an oxygen reduction electrode catalyst for a fuel cell.

[0002]

[Prior Art and Problems] Conventional electrolytic reduction of oxygen is
The production of superoxide by one-electron reduction and the production of hydrogen peroxide by two-electron reduction are the main ones, and the catalysts capable of producing water by four-electron reduction are not well known. . Since 4-electron reduction of oxygen can be generated at the highest potential, it can be used as an oxidizing agent with strong oxidizing power, and since it can provide a clean energy conversion system for water production, the development of a catalyst for it is desired. It was rare. For example, as a specific application example, a smooth platinum electrode is used in current fuel cells as an oxygen electrode that enables oxygen four-electron reduction under strong acidity. However, the overvoltage is large in the oxygen four-electron reduction system. Therefore, as a means for solving this energy loss, many electron transfer rate increasing agents, that is, electrode catalyst systems have been proposed. First, a solution method using a cobalt porphyrin binuclear complex has been attempted. However, the catalyst operating speed is slow, resulting in the oxygen reduction current remaining 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 clarified.

From the above circumstances, for example, the development of a catalyst system having an excellent action for the four-electron reduction of oxygen has been an extremely important issue. Therefore, the invention of this application enables oxygen four-electron reduction, which exceeds the conventional technical limits as described above, has a high oxygen reduction potential, high catalytic activity and excellent stability, and is easy to prepare. It is an object to provide a new copper binuclear complex.

[0004]

In order to solve the above-mentioned problems, the invention of this application makes it possible to reduce oxygen under acidic conditions by using a binuclear copper complex that reacts extremely easily with molecular oxygen. It is what That is, this application
The following inventions are provided.

First, the invention of this application is based on a binuclear copper complex.
A copper complex catalyst for oxygen reduction comprising a dinuclear copper complex
The two copper atoms are μ- bridged by an oxygen atom.
Oxo, μ-dioxo, μ-hydroxo, and di-μ
-In the form of at least one of hydroxo, and
Phenanthroline derivative or 1,4,7-triaz
It is attached to any ligand selected from clononane derivatives.
A copper complex catalyst for oxygen reduction, which is characterized by
To serve.

[0006] The invention of this application, the second, copper complex catalyst for the oxygen reduction, the binuclear copper complex oxide of 0~3V instead
Having an original potential, and thirdly, two
Copper atoms of the same or different, 0 valence, 1 valence, 2 valence,
States that it is a copper complex catalyst having a trivalent valence.
It is something like.

[0007] Then, in the fourth invention of this application, acid
A four-electron reduction method of oxygen, comprising:
Acidic solution containing any of the copper complex catalysts for oxygen reduction
, Electrolytic reduction at the copper reduction potential of the oxygen-reducing copper complex
An oxygen reduction method characterized by the above is also provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application will be described in detail below. The basic feature of the catalyst of the present invention is that it is a binuclear copper complex and that it has an oxidation potential of -1 to 2V. More specifically, as a feature,
As mentioned above, two copper atoms are bridged by an oxygen atom, more typically μ-oxo, μ-dioxo, μ-
It is shown to take the form of at least one of hydroxo and di-μ-hydroxo, that the mononuclear copper complex is formed by reaction with molecular oxygen, and the like.

In the constitution as a complex, in terms of the ligand, for example, the ligand is 1,10-phenanthroline.
A binuclear complex composed of a phenanthroline derivative such as or 1,4,7-triazacyclononane, where two copper atoms are bridged by an oxygen atom is indicated as suitable.

In the copper binuclear complex system of the present invention, the number of copper valences is also important. The valence of copper is 0, 1, 2, 3
Valences or mixed valences thereof are suitable. The catalyst of the present invention, for example, the μ-oxo type binuclear complex provided by the present invention exhibits higher 4-electron reduction activity than the mononuclear copper complex. The copper binuclear complex of the present invention is exemplified by μ
-Oxobis (1,10-phenanthroline copper (II))
Chloride, μ-oxobis (5-methyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-dimethyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,4) 7-Dimethyl-1,10-phenanthroline copper (II)) chloride, μ
-Oxobis (5,6-dimethyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5-ethyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-diethyl) -1,10-Phenanthroline copper (II)) chloride, μ-oxobis (4,7-diethyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5,6-diethyl-1,10-phenanthroline Copper (II)) chloride, μ
-Oxobis (5-propyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-dipropyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,7-dipropyl) -1,10
-Phenanthroline copper (II)) chloride, μ-oxobis (5,6-dipropyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5-isopropyl-1,10-phenanthroline copper (II)) chloride ,
μ-oxobis (2,9-diisopropyl-1,10-
Phenanthroline copper (II)) chloride, μ-oxobis (4,7-diisopropyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5,6-diisopropyl-1,10-phenanthroline copper (II)) Chloride, μ-oxobis (5-n-butyl-1,10-)
Phenanthroline copper (II)) chloride, μ-oxobis (2,9-n-butyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,7-n-butyl-1,10-phenanthroline copper (II)) chloride,
μ-oxobis (5,6-n-butyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5, t-butyl-1,10-phenanthroline copper (I)
I)) chloride, μ-oxobis (2,9-t-butyl-1,10-phenanthroline copper (II)) chloride, μ
-Oxobis (4,7-t-butyl-1,10-phenanthrolinecopper (II)) chloride, μ-oxobis (5,5)
6-t-butyl-1,10-phenanthroline copper (I
I)) chloride, μ-oxobis (5-phenyl-1,
10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-diphenyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,7-diphenyl-1,10-phenanthroline copper (II) )) Chloride, μ-oxobis (5,6-diphenyl-1,10
-Phenanthroline copper (II)) chloride, μ-oxobis (5-benzyl-1,10-phenanthroline copper (I
I)) chloride, μ-oxobis (2,9-dibenzyl-1,10-phenanthroline copper (II)) chloride, μ
-Oxobis (4,7-dibenzyl-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5,5)
6-Dibenzyl-1,10-phenanthroline copper (I
I)) chloride, μ-oxobis (5-chloro-1,1)
0-phenanthroline copper (II)) chloride, μ-oxobis (2,9-dichloro-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,7-dichloro-1,10-phenanthroline copper (II) )) Chloride,
μ-oxobis (4,7-dichloro-1,10-phenanthrolinecopper (II)) chloride, μ-oxobis (5,5)
6-Dichloro-1,10-phenanthroline copper (II))
Chloride, μ-oxobis (5-bromo-1,10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-dibromo-1,10-phenanthroline copper (II)) chloride, μ-oxobis (4,4) 7-dibromo-1,10-phenanthroline copper (II)) chloride, μ
-Oxobis (5,6-dibromo-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5-nitro-1,10-phenanthroline copper (II)) chloride, μ-oxobis (2,9-dinitro) -1,10-Phenanthroline copper (II)) chloride, μ-oxobis (4,7-dinitro-1,10-phenanthroline copper (II)) chloride, μ-oxobis (5,6-dinitro-1,10-phenanthroline Copper (II)) chloride, μ
-Oxobis ((1,10-phenanthroline) -5-
Copper (II) carboxylic acid chloride, μ-oxobis ((1,10-phenanthroline) -2,9-dicarboxylic acid copper (II)) chloride, μ-oxobis ((1,10
-Phenanthroline) -4,7-dicarboxylic acid copper (I
I)) chloride, μ-oxobis ((1,10-phenanthroline) -5,6-dicarboxylic acid copper (II)) chloride, μ-oxobis ((1,10-phenanthroline)
-5-carboxamide copper (II)) chloride, μ-oxobis ((1,10-phenanthroline) -2,9-dicarboxamide copper (II)) chloride, μ-oxobis ((1,10-phenanthroline) -4, 7-dicarboxamide copper (II)) chloride, μ-oxobis ((1,
10-phenanthroline) -5,6-dicarboxamide copper (II)) chloride, μ-oxobis (methyl (1,1)
0-phenanthroline) -5-carboxylic acid ester copper (II)) chloride, μ-oxobis (dimethyl (1,1)
0-phenanthroline) -2,9-dicarboxylic acid ester copper (II)) chloride, μ-oxobis (dimethyl (1,10-phenanthroline) -4,7-dicarboxylic acid ester copper (II)) chloride, μ-oxobis ( Dimethyl (1,10-phenanthroline) -5,6-dicarboxylic acid ester copper (II)) chloride, μ-oxobis (ethyl (1,10-phenanthroline) -5,6-carboxylic acid ester copper (II)) chloride, μ-oxobis (diethyl (1,10-phenanthroline) -2,9-
Dicarboxylic acid ester copper (II)) chloride, μ-oxobis (diethyl (1,10-phenanthroline) -4,
7-Dicarboxylic acid ester copper (II)) chloride, μ-oxobis (diethyl (1,10-phenanthroline)-
Μ-oxo binuclear copper complex such as 5,6-dicarboxylic acid ester copper (II)) chloride, μ-hydroxobis (bis (1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (Bis (5-methyl-1,10
-Phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-dimethyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4 , 7-Dimethyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-dimethyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5-ethyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (2,9
-Diethyl-1,10-phenanthroline) copper (II))
Perchlorate, μ-hydroxobis (bis (4,7-diethyl-1,10-phenanthroline) copper (II)) Perchlorate, μ-hydroxobis (bis (5,6-diethyl-
1,10-phenanthroline) copper (II)) perchlorate,
μ-hydroxobis (bis (5-propyl-1,10-
Phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-dipropyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4,4) 7-dipropyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-dipropyl-1,10-phenanthroline) copper (II)) perchlorate, μ -Hydroxobis (bis (5-isopropyl-1,10-phenanthroline)
Copper (II)) perchlorate, μ-hydroxobis (bis (2,9-diisopropyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4,7- Diisopropyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-diisopropyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxo Bis (bis (5-n-butyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,2
9-n-butyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (4,7
-N-Butyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (5,6
-N-Butyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (5, t
-Butyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-t-butyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4,7-t-butyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-t-butyl-
1,10-phenanthroline) copper (II)) perchlorate,
μ-hydroxobis (bis (5-phenyl-1,10-
Phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-diphenyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4,4) 7-diphenyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-diphenyl-1,10-phenanthroline) copper (II)) perchlorate, μ -Hydroxobis (bis (5-dibenzyl-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,2
9-dibenzyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (4,7
-Dibenzyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (5,6
-Dibenzyl-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (5-chloro-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-dichloro-)
1,10-phenanthroline) copper (II)) perchlorate,
μ-hydroxobis (bis (4,7-dichloro-1,1
0-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (5,6-dichloro-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis ( 5-Bromo-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (2,9-dibromo-1,10-phenanthroline) copper (II)) perchlorate, μ -Hydroxobis (bis (4,
7-dibromo-1,10-phenanthroline) copper (I
I)) perchlorate, μ-hydroxobis (bis (5,6
-Dibromo-1,10-phenanthroline) copper (II))
Perchlorate, μ-hydroxobis (bis (5-nitro-
1,10-phenanthroline) copper (II)) perchlorate,
μ-hydroxobis (bis (2,9-dinitro-1,1
0-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis (4,7-dinitro-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis ( 5,6-Dinitro-1,10-phenanthroline) copper (II)) perchlorate, μ-hydroxobis (bis ((1,10-phenanthroline) -5-carboxylic acid) copper (II)) chloride, μ -Hydroxobis (bis ((1,10-phenanthroline) -2,9-carboxylic acid) copper (II)) chloride, μ-hydroxobis (bis ((1,10-phenanthroline) -4,7-dicarboxylic acid) Copper (II)) chloride, μ-hydroxobis (bis ((1,10-phenanthroline) -5,6-dicarboxylic acid) copper (II)) chloride, μ-hydroxobis (bis ((1,10-phenanthroline) ) -5-Carboxamido) copper (II)) chloride, μ-hydroxobis (bis ((1,10-phenanthroline) -2,9-dicarboxamido) copper (II)) chloride, μ-hydroxobis (bis ( (1,10-phenanthroline) -4,7-dicarboxamido) copper (II)) chloride, μ-hydroxobis (bis ((1,10-phenanthroline) -5,6
-Dicarboxamido) copper (II)) chloride, μ-hydroxobis (bis (methyl (1,10-phenanthroline) -5-carboxylic acid ester) copper (II)) chloride,
μ-hydroxobis (bis (dimethyl (1,10-phenanthroline) -2,9-dicarboxylic acid ester) copper (II)) chloride, μ-hydroxobis (bis (dimethyl (1,10-phenanthroline) -4,7 -Dicarboxylic acid ester) copper (II)) chloride, μ-hydroxobis (bis (dimethyl (1,10-phenanthroline)-
5,6-dicarboxylic acid ester) copper (II)) chloride,
μ-hydroxobis (bis (ethyl (1,10-phenanthroline) -5-carboxylic acid ester) copper (II)) chloride, μ-hydroxobis (bis (diethyl (1,1
0-phenanthroline) -2,9-dicarboxylic acid ester) copper (II)) chloride, μ-hydroxobis (bis (diethyl (1,10-phenanthroline) -4,7-
Dicarboxylic acid ester) copper (II)) chloride, μ-hydride
Loxobis (bis (diethyl (1,10-phenanthro
Phosphorus) -5,6-dicarboxylic acid ester) copper (II))
Μ-Hydroxo copper binuclear complex such as lolide , di-μ- hydroxobis (1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-methyl-1,10)
-Phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-dimethyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-dimethyl-1,10) -Phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6-
Dimethyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-ethyl-1,10)
-Phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-diethyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-diethyl-1,10) -Phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6-
Diethyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-propyl-1,1)
0-phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-dipropyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-dipropyl-1, 10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6
-Dipropyl-1,10-phenanthroline copper (II))
Chloride, di-μ-hydroxobis (5-isopropyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-diisopropyl-1,
10-phenanthroline copper (II)) chloride, di-μ-
Hydroxobis (4,7-diisopropyl-1,10-
Phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6-diisopropyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-n-butyl-1,10-) Phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-
Di-n-butyl-1,10-phenanthroline copper (I
I)) Chloride, di-μ-hydroxobis (4,7-di-n-butyl-1,10-phenanthroline copper (II))
Chloride, di-μ-hydroxobis (5,6-di-n-
Butyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5, t-butyl-1,1
0-phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-di-t-butyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-) Di-t-butyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6-di-t-butyl-1,10-phenanthroline copper (II)) chloride, di-μ -Hydroxobis (5-
Phenyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-diphenyl-
1,10-phenanthroline copper (II)) chloride, di-
μ-hydroxobis (4,7-diphenyl-1,10-
Phenanthroline copper (II)) chloride, di-μ-hydroxobis (5,6-diphenyl-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-benzyl-1,10-phenanthroline copper) (I
I)) chloride, di-μ-hydroxobis (2,9-dibenzyl-1,10-phenanthrolinecopper (II)) chloride, di-μ-hydroxobis (4,7-dibenzyl-
1,10-phenanthroline copper (II)) chloride, di-
μ-hydroxobis (5,6-dibenzyl-1,10-
Phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-chloro-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (2,9-
Dichloro-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-dichloro-
1,10-phenanthroline copper (II)) chloride, di-
μ-hydroxobis (5,6-dichloro-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-bromo-1,10-phenanthroline copper (II)) chloride, di-μ- Hydroxobis (2,9-
Dibromo-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-dibromo-
1,10-phenanthroline copper (II)) chloride, di-
μ-hydroxobis (5,6-dibromo-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (5-nitro-1,10-phenanthroline copper (II)) chloride, di-μ- Hydroxobis (2,9-
Dinitro-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis (4,7-dinitro-
1,10-phenanthroline copper (II)) chloride, di-
μ-hydroxobis (5,6-dinitro-1,10-phenanthroline copper (II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -5-carboxylic acid copper (II)) chloride, di -Μ-hydroxobis ((1,10-phenanthroline) -2,9-dicarboxylic acid copper (II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -4,7-dicarboxylic acid copper ( II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -5,6-dicarboxylic acid copper (II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -5- Carboxamide copper (II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -2,9-dicarboxamide copper (II)) chloride, di-μ-hydroxo ((1,10-phenanthroline) -4,7-dicarboxamide copper (II)) chloride, di-μ-hydroxobis ((1,10-phenanthroline) -5,6-dicarboxamide copper (II)) chloride, Di-μ-hydroxobis (methyl (1,10-phenanthroline) -5-carboxylic acid ester copper (II)) chloride, di-μ-hydroxobis (dimethyl (1,10-phenanthroline) -2,
9-dicarboxylic acid ester copper (II)) chloride, di-μ
-Hydroxobis (dimethyl (1,10-phenanthroline) -4,7-dicarboxylic acid ester copper (II)) chloride, di-μ-hydroxobis (dimethyl (1,10-
Phenanthroline) -5,6-dicarboxylic acid ester copper (II)) chloride, di-μ-hydroxobis (ethyl (1,10-phenanthroline) -5-carboxylic acid ester copper (II)) chloride, di-μ-hydroxo Bis (diethyl (1,10-phenanthroline) -2,9-dicarboxylic acid ester copper (II)) chloride, di-μ-hydroxobis (diethyl (1,10-phenanthroline)-
4,7-Dicarboxylic acid ester copper (II)) chloride, di-μ-hydroxobis (diethyl (1,10-phenanthroline) -5,6-dicarboxylic acid copper (II))
Chloride, di-μ-hydroxobis (1,4,7-tri
Azacyclononane copper (II)) trifluoromethanesulfo
Phosphate, di-μ-hydroxobis (1,4,7-trimethyl-1,4,7-triazacyclononane copper (II)) trifluoromethanesulfonate, di-μ-hydroxobis (1,4 , 7-Triethyl-1,4,7-triazacyclononane copper (II)) trifluoromethanesulfonate, di-μ-hydroxobis (1,4,7-tripropyl-1,4,7-triaza Cyclononane copper (II)) trifluoromethane sulfonate, di-μ-hydroxobis (1,4,7-tri-n-butyl-1,4,7-triazacyclononane copper (II)) trifluoromethane sulfone Acid salt, di-μ-hydroxobis (1,4,7-tri-t
-Butyl-1,4,7-triazacyclononane copper (I
I)) trifluoromethanesulfonate, di-μ-hydroxobis (1,4,7-triphenyl-1,4,7-
Triazacyclononane copper (II)) trifluoromethanesulfonate, di-μ-hydroxobis (1,4,7-tribenzyl-1,4,7-triazacyclononane copper (I
I)) Di-μ-hydroxo copper binuclear complexes such as trifluoromethanesulfonate.

In the copper complex catalyst of the present invention, monovalent to trivalent valence conversion of the central metal copper plays a role of catalytic activity, and the ligand mainly contributes to regulation of redox potential. Is also a feature. Since the oxygen reduction catalyst of the present invention has a clear structure and has high selectivity for 4-electron reduction, it is also suitable as an oxygen oxidation catalyst for organic compounds such as phenol and dithiol. Further, it can be used as an electrode catalyst by fixing the catalyst on the surface of the electrode by various methods.

[0012] oxygen reduction catalyst of the present invention, 4 addition it is possible to control the electronic processes, such as oxygen, such as the presence of active oxygen is undesirable oxidation reactions, with a high potential (the thermodynamic potential near the oxygen four-electron reduction) Can be used for purposes such as oxygen reduction of
It Hereinafter, the present invention will be described in more detail with reference to examples.

[0013]

Example 1 0.41 g of ammonium hexafluorophosphate was dissolved in 25 ml of ultrapure water, and perchloric acid was added dropwise to 0.5M while stirring at room temperature under a stream of pure water argon. After stirring this at room temperature for about 10 minutes, it was moved to a three-chamber electrochemical cell under an argon stream, sealed, and then dissolved in 5 μl of an acetonitrile solution in which the system was replaced with oxygen gas, μ−
Oxobis (1,10-phenanthroline copper (II)) chloride complex (1 mM) was applied to the electrode by spin coating.

In the electrolysis, a glassy carbon disk electrode, a platinum ring electrode, a platinum wire electrode as a counter electrode, and a saturated calomel electrode as a reference electrode are used for the working electrode, and the disk electrode potential is swept to set the oxygen reduction potential and simultaneously generated. It was detected by oxidizing hydrogen peroxide independently with a ring electrode set to a constant potential. The measurement was performed by both a static system (cyclic voltammetry) and a convection system (rotating ring disc voltammetry), and the detected current was recorded on a graph paper using an XY recorder.

As a result of the detection measurement, a reduction current derived from oxygen four-electron reduction was detected on the disk at -0.20V.
The current value of hydrogen peroxide detected at the ring electrode was very small. The capture rate N due to the shape of the disk electrode in the rotating ring used was determined to be 0.36 using the ferrocyan / ferrician redox couple. In the argon atmosphere, the above reduction current derived from oxygen reduction is not observed. The selectivity of 4-electron reduction was determined to be 90% or more from the value of the capture rate in an oxygen atmosphere. Example 2 0.41 g of ammonium hexafluorophosphate was dissolved in 25 ml of ultrapure water, and perchloric acid was added dropwise to 0.5M while stirring at room temperature in a pure water argon stream. After stirring this at room temperature for about 10 minutes, it was moved to a three-chamber electrochemical cell under an argon stream and sealed, and then the system was replaced with oxygen gas and dissolved in 5 μl of a dichloromethane solution.
-Hydroxobis (1,4,7-tribenzyl-1,
4,7-Triazacyclononane copper (II)) trifluoromethanesulfonate complex (1 mM) was applied to the electrode by spin coating.

In the electrolysis, a glassy carbon disk electrode, a platinum ring electrode, a platinum wire electrode as a counter electrode, and a saturated calomel electrode as a reference electrode are used for the working electrode, and the disk electrode potential is swept to set the oxygen reduction potential and simultaneously generated. It was detected by oxidizing hydrogen peroxide independently with a ring electrode set to a constant potential. The measurement was performed by both a static system (cyclic voltammetry) and a convection system (rotating ring disc voltammetry), and the detected current was recorded on a graph paper using an XY recorder.

As a result of the detection measurement, a reduction current derived from oxygen four-electron reduction at -0.08 V was detected on the disk.
The current value of hydrogen peroxide detected at the ring electrode was very small. In the argon atmosphere, the above-mentioned reduction current derived from oxygen reduction was not observed, and the selectivity of 4-electron reduction was 90%.
It was decided as above. Example 3 0.55 g of 2,6-dimethylphenol was added to 8 m of toluene.
2 ml of isopropyl alcohol containing 0.009 g of sodium hydroxide dissolved in 1 was added. Next, 0.065 g of μ-oxobis (1,10-phenanthroline copper (II)) chloride complex was dissolved in 5 ml of toluene and stirred while passing oxygen. The monomer solution prepared above was slowly added dropwise to this solution, and the mixture was stirred for 2 hours while passing oxygen, and then the reaction solution was added with 300 m of methanol containing 5 wt% of hydrochloric acid.
It was dripped at 1. The precipitate was filtered, washed with methanol, dissolved in 30 ml of chloroform, and reprecipitated in hydrochloric acid-methanol. The white precipitate was filtered and vacuum dried to obtain poly (2,6-dimethyl-1,4-phenylene oxide) in a yield of 80% or more.

[0018]

INDUSTRIAL APPLICABILITY The oxygen reduction catalyst of the present invention can promote oxygen oxidation of an organic compound by utilizing it as a homogeneous catalyst, and can generate high potential with water generation by selective four-electron oxidation. Can be pulled out. Also,
The use as a heterogeneous electrode surface catalyst greatly contributes to the use as an oxygen reduction electrode of a fuel cell, an oxygen sensor and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-181032 (JP, A) JP-A-7-278152 (JP, A) JP-A-10-45903 (JP, A) Yosuke Kumaki et al. 3 Name, Redox and Oxygen Four-Electron Process of μ-oxo Double Encoded Copper Complexes with Bipyridine Coordinator, Proceedings of Lecture of 1998 Chemical Society of Japan 74th Spring Annual Meeting 1998, The Chemical Society of Japan, March 1998 14th, 23 (58) Fields surveyed (Int.Cl. ⁷ , DB name) B01J 21/00-38/74 CA (STN)

Claims (4)

(57) [Claims] 1. A copper complex catalyst for oxygen reduction comprising a binuclear copper complex.
The two copper atoms in the binuclear copper complex are oxygen and oxygen.
Mu-oxo, mu-dioxo, mu- bridged by atoms
Hydroxo, and less of di-μ-hydroxo
Both are in the form of a phenanthroline derivative or
Is selected from 1,4,7-triazacyclononane derivatives
Is coordinated to one of the ligands
Copper complex catalyst for oxygen reduction . 2. The binuclear copper complex has a redox potential of 0 to 3 V.
The copper complex catalyst for oxygen reduction according to claim 1 . 3. Two copper atoms are the same or different and are 0.
Claim 1 having a valence of 1, valence 1, valence 2, or valence 3.
Or a copper complex catalyst according to any one of 2 above . 4. A four-electron reduction method of oxygen, which comprises:
Is at least the oxygen reduction according to any one of claims 1 to 3.
A copper complex for reducing oxygen in an acidic solution containing a copper complex catalyst
Oxygen characterized by electrolytic reduction at the reduction potential of body copper
How to reduce .