JP2003109614A - Catalyst for high molecular solid electrolyte fuel cell oxygen pole and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for an inexpensive high molecular solid electrolyte fuel cell oxygen pole and a method of manufacturing the same, capable of exercising the catalyst characteristic similar to a conventional catalyst using a large amount of platinum. SOLUTION: In this catalyst for high molecular solid electrolyte-type fuel cell oxygen pole and the method of manufacturing the same, the catalyst is composed of carbon material holding a large ring compound complex of transition metal and noble metal, and a BET specific surface area of the carbon material is 500 m<2> /g or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer solid oxide fuel cell oxygen electrode catalyst, and more particularly to a high performance and inexpensive polymer solid electrolyte fuel cell oxygen electrode catalyst.

[0002]

2. Description of the Related Art Polymer solid oxide fuel cells are capable of extracting a high current density, capable of operating at low temperatures, and can be designed as a compact battery. Therefore, they are used as power sources for electric vehicles and portable electronic devices. It is expected to be applied as a stationary power source such as a mold power source or a household power source, and studies for practical use are being vigorously pursued.

In order to put the polymer solid oxide fuel cell into practical use, a catalyst for accelerating the reaction is indispensable. As the catalyst, platinum or platinum alloy is mainly studied for both hydrogen electrode and oxygen electrode. (For example, the 2000 New Energy and Industrial Technology Development Organization commissioned research result report “Development of low cost solid polymer fuel cell electrodes”). However, the overvoltage is particularly large at the oxygen electrode, and when a current in the practical range of about 1 A / cm ^{2 is} to be extracted with respect to the theoretical output voltage of 1.23 V of a single cell, a normal catalyst loading amount (0. The overvoltage of the oxygen electrode reaches 0.3 V or more at 1 to 0.5 mg / cm ² (see Heisei 1
Report of research results commissioned by Japan New Energy and Industrial Technology Development Organization "Fundamental Research on Ion Exchange Membrane for Practical Use of Highly Durable Batteries") As a measure to reduce the overvoltage, it is possible to increase the amount of platinum or platinum alloy used for the catalyst, but the effect of reducing the overvoltage by increasing the amount of catalyst is small, while the problem of cost increase due to the increase of the catalyst is more As the cost increases, the balance between cost and catalyst performance remains a major issue.

As described above, a new catalyst that substitutes platinum for reducing cost and overvoltage is desired, and vigorous research is being conducted. Among them, as a catalyst having an oxygen reducing ability, a complex of a macrocyclic compound containing a metal such as porphyrin (PP), phthalocyanine (Pc) and tetraazaannulene (TAA) has been studied for a long time (H. Jahnke, M. Schonborn,
G. Zimmermann, Topics in Cu
rent Chemistry, Vol. 61, p
133-181 (1976)). Macrocyclic compound complexes of these metals are known as mediators of oxygen in the living body, that is, the basic idea is to apply them to electrochemical reduction reaction of oxygen molecules by utilizing their adsorption ability for oxygen molecules. Makoto Yuasa, Journal of Japan Oil Chemists' Society, Vo
l. 49, p315-323, (2000)). At the beginning of the research, studies were conducted aiming at practical use as a catalyst for oxygen electrodes of phosphoric acid fuel cells, but problems such as catalyst deterioration due to phosphoric acid and lower catalytic activity than platinum remain, and Application to acid fuel cells has not been achieved. On the other hand, in the case of the solid polymer electrolyte fuel cell, it is considered that the deterioration of the catalyst in an acidic environment can be avoided, and thus new energetic research is progressing in recent years.

In order to apply these metal complexes of macrocyclic compounds as catalysts to practical electrodes, it is essential to immobilize the catalysts on electron conductors. A carbon support is used for this purpose. Specifically, carbon black having a high electron conductivity and a large surface area is used. The combination of the carbon support and the metal macrocycle complex enables continuous use as an electrode catalyst.

The problems as the oxygen reduction catalyst of the metal complex of the macrocyclic compound supported on these carbon carriers are that the overvoltage is larger than that of the platinum catalyst, and that the reduction product is only water (called 4-electron reaction product). Rather, it is a mixture of hydrogen peroxide (called a two-electron reaction product). As a countermeasure against overvoltage, heat treatment in a non-oxidizing atmosphere has been proposed (J.A.R. van Veen e).
t al. , J. Chem. Soc. , Farad
ay Trans. 1, Vol. 77, p2827
(1981)). However, the improved overvoltage after heat treatment is 0.1 V or more as compared with platinum, and a problem remains in practical use.

In order to improve the yield of the four-electron reaction product, a binuclear complex (Japanese Patent Laid-Open No. 11-253811, F.
C. Anson et al. , Journal of of
American Chemical Societ
y, Vol. 113, p9564 (1991)),
Dimerization of Porphyrin Complex (JP Collman
et al. , Journal of American
Chemical Society, Vol. 10
2, p6027 (1980)) and the like have been proposed.
However, there remain problems that industrial application such as yield in synthesis is difficult, cost is high, and overvoltage is large as compared with platinum or platinum alloy.

On the other hand, the development of a catalyst aimed at reducing the amount of platinum used by making fine platinum particles or improving the utilization rate of the platinum catalyst, that is, cost reduction is under consideration (for example,
FY 2000 New Energy and Industrial Technology Development Organization Contract Research Results Report "Development of low cost solid polymer fuel cell electrodes"). However, a problem remains in practical use due to a decrease in output characteristics accompanying a reduction in the amount of platinum used.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides an inexpensive catalyst for a polymer solid oxide fuel cell oxygen electrode that exhibits catalytic characteristics equivalent to those of a conventional catalyst that uses a large amount of platinum, and a method for producing the same. To aim.

[0010]

In order to solve the above-mentioned problems, the inventors of the present invention have made earnest studies, and as a result, have succeeded in solving the problems by the following means, resulting in the present invention. That is, (1) a catalyst comprising a carbon material supporting a macrocyclic compound complex of a transition metal and a noble metal, wherein the BE of the carbon material is
A polymer solid oxide fuel cell oxygen electrode catalyst having a T specific surface area of 500 m ² / g or more. (2) The carbon material is S _BET −S _CTAB ≧ 100 m ² /
The polymer solid oxide fuel cell oxygen electrode catalyst according to (1), which satisfies g. (3) The polymer solid oxide fuel cell oxygen electrode catalyst according to (1), wherein the macrocyclic compound has a cyclic structure of N ₄ -chelate structure. (4) The catalyst for oxygen electrode of polymer solid oxide fuel cell according to (1), wherein the transition metal is Co and / or Fe. (5) The catalyst for a polymer solid oxide fuel cell oxygen electrode according to (1), wherein the noble metal contained in the catalyst is 5% by mass or less. (6) The polymer solid oxide fuel cell oxygen electrode catalyst according to (1), wherein the transition metal contained in the catalyst is 2% by mass or less. (7) A polymer characterized by carrying out heat treatment at a temperature of 700 ° C to 1100 ° C after supporting a transition metal-containing macrocyclic compound and a noble metal on the surface of carbon powder having a BET specific surface area of 500 m ² / g or more. A method for producing a catalyst for an oxygen electrode of a solid oxide fuel cell.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be specifically described below.

Essentially important in the present invention is that
(i) to develop a catalytic action by allowing a macrocyclic compound complex of a transition metal and a noble metal to coexist, (ii) using a carbon material having a large specific surface area as a carrier for supporting the above-mentioned catalyst,
There are two points.

Here, the macrocyclic compound is composed of 9 atoms or more and has 3 or more coordination bonds (ligati).
ng) is a cyclic compound having an atom (Coordin
ation Chemistry of Macrocy
CLIC COMPUNDS, G.I. A. Melso
n, Plenum press, New York &
London, (1979)), and its specific structure is phthalocyanines, porphyrins, azaporphyrins, tetraazaannulene, Schiff.
N ₄ -chelate structure such as base, N ₂ O ₂ -chelate structure such as N, N (-ethylenebis (salicylideneiminato), N ₂ S ₂ -chelate structure such as compounds derived from orthoaminophenol , A macrocyclic compound such as an O ₄ -chelate structure such as a compound derived from salicylaldehyde, etc. Any of these macrocyclic compounds are applicable to the present invention, but preferably a metal Against 4
A compound having a complex-forming ability of coordination or higher is preferable. This is because as the coordination number increases, the chemical stability of the complex increases, that is, the catalyst life increases.

The need for the centrally located metal of the macrocycle to be a transition metal lies in its electronic structure. That is, the charge transfer from the bond orbit of the oxygen molecule to the empty s orbit of the metal atom at the adsorption site and the charge transfer from the d orbit of the transition metal atom to the antibond orbit of the oxygen molecule. , The adsorption state of oxygen molecules and macrocycle complexes centered on transition metal atoms is stabilized (Kobayashi, K., Yamaguchi, K., Surface, Vol. 2).
3, p311 (1985)), and as a result, shows high oxygen reduction activity. That is, a transition metal having an empty orbit in the d electron orbit basically satisfies the requirement for oxygen reduction activity.

In the composite catalyst of the present invention in which a macrocycle of a transition metal and a noble metal coexist, the coexistence state of the catalyst is greater than the catalytic activity of each of them, as will be shown in the specific examples below. It is based on the experimental fact that the activity is high. Although its theoretical interpretation is uncertain, for example, along with the 4-electron reduction reaction on the noble metal, the 2-electron reaction on the macrocyclic compound complex of the transition metal is followed by a further 2-electron reduction reaction on the precious metal. Since the oxygen reduction reaction is carried out by two reduction reaction paths such as those described above, it is presumed that the catalytic activity is promoted more when they coexist than when they each coexist.

Further, in order to improve the catalytic activity due to the coexistence of these two catalysts, it is an essential condition that the surface area of the carbon material which is the carrier of the catalyst is large. As for the effect of the catalyst carrier, not only the physical effect of broadening the field of the reaction but also the activation of the catalytic action through the chemical interaction of the transition metal complex with the macrocyclic compound is presumed. In the catalytic reaction process of transition metal macrocycle complex, the reduction reaction of oxygen molecules adsorbed on the transition metal is accompanied by the valence change of the transition metal at the same time, but facilitates (promotes) the valence change.
Is the π electron of the macrocyclic compound. That is, the valence of the transition metal increases at the time of oxygen reduction, but in order to restore the catalytic ability, there is a process of returning the increased valence to the original (supplying electrons to the metal from the macrocyclic compound surrounding the metal). , Cannot exert continuous catalytic action. The electron transfer in this case is carried out by the π-electron system of the macrocyclic compound which is chelated to the transition metal atom. Further, it is a carrier of a carbon material forming a huge π-electron system that further facilitates the transfer of π-electrons of the macrocyclic compound.

Carbon materials having a large surface area are generally highly active. The activity is due to irregularities formed on the surface of the carbon material, defects on the carbon net surface due to fine pores, edge portions, and the like. In the present invention, by using a carbon material having a large surface area (high activity) as a carrier for a macrocyclic compound, the interaction between the π-electron system of the carbon material and the π-electron system of the macrocyclic compound is amplified. is there.

As a result of extensive studies, it was found that the specific surface area (BET specific surface area) obtained by the BET-type evaluation of the adsorption isotherm of nitrogen gas is appropriate as an index of the surface area corresponding to the catalytic activity. It was The specific numerical range is 500 m ² / g or more. If the amount is less than 500 m ² / g, the amount of the carbon surface irregularities, the carbon network surface defects due to fine pores, and the edge portion, which are presumed to amplify the catalytic activity, is insufficient, and the catalytic activity is not improved. On the other hand, 20
When the surface area is increased to 00 m ² / g or more, fine pores that penetrate deeply into carbon are formed, and the internal surface of the fine pores occupies a large proportion of the whole reaction field, so that mass transfer such as oxygen diffusion occurs. There is a possibility that the rate becomes rate-determining and the catalytic activity is deteriorated, which is not preferable in the present invention.

The specific surface area ratio of the fine pores is S _BET -S _CTAB ≧ 100 m ² / g. Where S _BET is the BET specific surface area and S _CTAB is the CTA.
The surface area defined by the amount of B (cetyltrimethylammonium bromide) adsorbed, which corresponds to the surface area excluding the micropores in which CTAB cannot enter. The measuring method is ASTM
According to the American Society for Testing and Materials D3765 method. As described above, the unevenness of the carbon surface, the defects on the carbon network surface due to the micropores, and the amount of the edge portion are considered to be the controlling factors of the catalytic activity, and therefore it is presumed that the optimum amount of the micropores exists. A quantitative expression of this is S _BET −S _CTAB ≧ 100 m ² / g.
When S _BET -S _CTAB is less than 100 m ² / g, the amount of micropores is small and the effect of amplifying the catalytic activity is small. On the other hand, S _BET −
If S _CTAB exceeds 1000 m ² / g, the ratio of the internal area of the micropores to the total surface area is too high, and the above-mentioned mass transfer of oxygen molecules is rate-determining, which may deteriorate the catalytic activity. It may not be preferred for the present invention.

The carbon material preferably used in the present invention is not particularly limited as long as it satisfies the above surface structure. For example, so-called conductive grade carbon black, carbon nanotubes, carbon nanofibers and the like can be mentioned.

The macrocyclic compound preferably used in the present invention preferably has an N ₄ -chelate structure. The extent of improvement in catalytic activity due to the coexistence of a transition metal macrocyclic compound complex and a noble metal depends on the level of the catalytic activity of the applied transition metal macrocyclic compound complex alone, that is, the catalyst of the macrocyclic compound complex. The higher the activity, the greater the effect of amplifying the catalytic activity due to the coexistence with the noble metal. It was also found that the N ₄ -chelate structure has higher catalytic activity than other chelate structures and can be suitably used in the present invention. Among the N ₄ -chelate structures, porphyrin derivatives such as tetraphenylporphyrin and tetramethoxyphenylporphyrin, phthalocyanine derivatives, and tetraazaannulene are particularly preferred because of their high catalytic activity.

The catalytic activity also changes depending on the type of transition metal element. As a result of diligent studies by the present inventor, it is Co and / or Fe that exhibits high activity independently of the type of macrocyclic compound, and can be suitably used in the present invention.

The noble metal used in the present invention is ruthenium, rhodium, palladium, osmium, iridium, platinum,
It also means an alloy containing these as the main components. In the present invention, it is preferable to apply ruthenium, rhodium, palladium, osmium, iridium, platinum, and alloys containing these as the main components because of their high catalytic activity. It is more preferable to use platinum and an alloy containing platinum as a main component. Other precious metals are
The catalytic activity is lower than that of platinum, and the improvement of the catalytic activity due to the coexistence of the transition metal with the macrocyclic compound complex is recognized, but the improvement is small.

The supported amount of the noble metal of the present invention is preferably 5% by mass or less. When it is supported in an amount of more than 5% by mass, the catalytic action of the noble metal alone becomes relatively strong, and the increase in the catalytic activity due to the coexistence of the transition metal with the macrocyclic compound complex becomes small. Furthermore, considering the cost of the catalyst,
The amount of the noble metal supported is more preferably 4% by mass or less. Further, in order to exhibit the function as a catalyst, the amount of the noble metal supported is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

The amount of the transition metal macrocyclic compound supported on the transition metal is preferably 2% by mass or less, more preferably 1% by mass or less. When it is supported in an amount of more than 2% by mass, the catalytic action of the transition metal macrocyclic compound complex becomes relatively strong, and the increase in the catalytic activity due to the coexistence with the noble metal becomes small. Further, the amount of the transition metal supported is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more in order to exhibit the function as a catalyst.

The essence of the catalytic activity of the catalyst specified in the present invention is presumed to be the interaction between the surface of the carbon material and the macrocyclic compound complex of the transition metal through π electrons. Therefore, as a result of diligently studying the method for adjusting the catalyst with the aim of further strengthening the π-electron interaction, as a result of supporting the transition metal macrocyclic compound complex and the noble metal on the surface of the carbon powder, It was found that a highly active catalyst can be prepared by heat treatment at a temperature of 700 ° C to 1100 ° C in an atmosphere. Here, if the treatment is carried out in an oxidizing atmosphere, the carbon carrier and the macrocyclic compound will be consumed by oxidation, and the catalytic activity will be lost. Further, in the heat treatment at a temperature lower than 700 ° C., the π-electron interaction between the carbon support and the macrocyclic compound is not sufficient, and the catalytic activity is not expressed. On the other hand, heat treatment at a temperature higher than 1100 ° C. causes thermal decomposition of the macrocyclic compound, resulting in loss of catalytic activity.

The catalyst of the present invention is a conventional method for forming an electrode catalyst layer of a polymer electrolyte fuel cell, for example, a slurry of a catalyst and a polymer solid electrolyte solution is prepared and the slurry is prepared by using carbon paper. The present invention can be applied to the method of applying to, and the method of forming the catalyst layer is not particularly limited.

[0028]

[Examples] With respect to the catalyst specified in the present invention,
This will be specifically described.

(Carbon material carrier) Commercially available carbon black was used as the carbon material carrier for the catalyst. If granulated, it was ground in a mortar in advance and subjected to the following catalyst preparation. Carbon black used in Examples and Comparative Examples is Ketjen Black EC (manufactured by Lion Corporation, E
(Abbreviated as C), Ketjen Black EC600JD (manufactured by Lion Corporation, abbreviated as EC600JD), Printex XE2 (manufactured by Degussa Japan Co., Ltd., abbreviated as XE2), Color Black FW200 (manufactured by Degussa Japan Co., Ltd.) , FW200), Vulcan XC72R
(Cabot Corporation, abbreviated as XC72R), and EC20PTC (XC, manufactured by ElectroChem, USA)
72 carrying 20% by mass of platinum). Table 1 collectively shows the BET specific surface area, S _BET -S _CTAB , of these carbon blacks.

(Catalyst preparation method) Chloroplatinic acid hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed so as to be a predetermined mass% and used as a carrier in an aqueous solution diluted with water to an appropriate amount. After carbon black was added and sufficiently stirred, dispersion was allowed to proceed with an ultrasonic generator. An electric furnace (hydrogen gas ratio: 10 to 50% by volume) in which a hydrogen / argon mixed gas was passed through the precursor obtained by drying and solidifying the dispersion liquid with an evaporator.
At 300 ° C., the chloroplatinic acid was reduced.

A transition metal macrocyclic compound complex (commercially available reagent) is weighed so as to be a predetermined mass%, and N, N'-dimethylformamide (reagent special grade) or pyridine (reagent special grade). The carbon black (Pt-C) supporting platinum described above was added to a solution to which an appropriate amount of was added, and the mixture was sufficiently stirred, and further dispersion was promoted using an ultrasonic generator. While the dispersion was kept warm in an oil bath at 70 ° C., refluxed for 8 hours or more (under argon flow),
Pour into distilled water at least 5 times the amount of the dispersion while stirring,
The macrocyclic compound was fixed on Pt-C. afterwards,
The catalyst was separated and collected by vacuum filtration, washed again with distilled water at a temperature of about 60 ° C., and the catalyst was collected by vacuum filtration.
It was vacuum dried at 100 ° C.

The macrocyclic compounds used in Examples and Comparative Examples are phthalocyanine (abbreviated as Pc), 5,10,1.
5,20-tetraphenyl-21H, 23H-porphyrin (abbreviated as TPP) and 5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin (abbreviated as TMPP). Further, it was treated at a predetermined temperature for 1 hour in an argon gas atmosphere to obtain a catalyst for evaluation.

The preparation of the catalyst carrying only the transition metal macrocyclic compound complex was carried out only by carrying the transition metal macrocyclic compound complex, except for the above-mentioned platinum carrying process, while carrying only platinum. The catalyst was prepared according to only the platinum loading process, excluding the loading process of the transition metal macrocycle complex.

(Evaluation Method of Catalytic Activity) Preparation of Sample for Evaluation 15 mg of catalyst powder obtained by previously pulverizing the catalyst in a mortar and a polymer solid electrolyte solution (EC-manufactured by ElectroChem, USA)
NS-05; Nafion 5% by mass solution) (300 mg) and ethanol (300 mg) were placed in a sample bottle and stirred with a stirrer for 15 minutes using a stirrer to prepare a sufficiently kneaded slurry.

Preparation of Test Electrode The above-mentioned slurry was applied onto the disk electrode of the rotating ring disk electrode and dried to give a test electrode. The disk electrode is a cylinder made of glassy carbon and having a diameter of 6 mm, and the sample is applied to the bottom surface thereof. Coating amount is 0.03
It was adjusted to be mg. Further, the ring electrode is a platinum cylinder having an inner diameter of 7.3 mm and an outer diameter of 9.3 mm, and the rotating ring disc electrode is such that the disc electrode and the ring electrode are concentrically located, and between the disc electrode and the ring electrode, In addition, the outside of the ring electrode is insulated with Teflon (registered trademark) resin.

Evaluation method (with) Rotating ring disk evaluation device (RRD) for day thickness measurement
E-1) was used to evaluate the electrochemical activity of the catalyst. Solartron SI12 for electrochemical evaluation
Bipolar measurement was performed by using two 87 and controlling the ring electrode and the disk electrode independently. The electrolyte should be 0.
A 1N sulfuric acid aqueous solution was used, a SCE electrode was used as the reference electrode, and a Pt plate was used as the counter electrode. The evaluation conditions are as follows. The potential of the disk electrode of the electrode rotated at 2500 rpm was changed from 1.0 V (SCE standard) to -0.2 V in the electrolytic solution state in which oxygen gas was bubbled and oxygen was saturated.
(SCE standard) is swept at a speed of 10 mV / sec, at that time, the potential of the ring electrode is maintained at 1.1 V (SCE standard), and the time-dependent change of the current flowing through the disk electrode and the ring electrode is measured. A plot of the disk current and the ring current with respect to the electrode potential was obtained.

Overvoltage Evaluation Method From the above plot of disk potential and disk current, the potential (E _1/2 ) at a current value half the saturation current value was read. EC20, a catalyst manufactured by ElectroChem, USA
PTC, based on the E _1/2 ⁰ of (catalyst supported a 20 wt% platinum on carbon black), examples of each catalyst of Comparative Example ^{_{ΔE 1/2 = E 1/2 0 -E 1}} / ₂ was evaluated. That is, the larger ΔE _1/2 , the larger the overvoltage and the lower the catalytic activity. E at ΔE _1/2 = 0 (mV)
Overvoltage equivalent to C20PTC, if negative, EC2
It corresponds to a smaller overvoltage and a higher catalytic activity than 0 PTC.

Evaluation Method of 4-Electron Reaction Rate From the plot of the ring current and the disk current with respect to the disk potential, the 4-electron reaction rate η was calculated based on the following equation.

Η (%) = [I _d − (I _r / n)] / [I _d
+ (I _r / n)] where I _d is the disk current, I _r is the ring current,
n represents the capture rate of the disc reaction product by the ring electrode.

An experimental method for measuring the capture rate is described in Akira Fujishima, et al.
As a result of evaluation according to the electrochemical measurement method (bottom) and Gihodo Publishing (1991), in the electrode used in the example, n =
It was 0.36.

Further, η changes according to the disk potential (η becomes smaller as the potential becomes base), but in this evaluation, the disk potential was 0 V (SCE standard so that the difference in η due to the catalyst becomes clear. ) Was adopted.

In Table 1, (a) physical properties of the carrier, BET surface area, CTAB surface area, (b) catalyst composition, macrocyclic compound species, transition metal species and their loading amount, platinum loading amount,
(C) As the catalyst preparation conditions, the heat treatment temperature after supporting the catalyst,
(D) As an index of catalytic activity, the overvoltage difference ΔE _1/2 and the four-electron reaction rate η with respect to EC20PTC are shown together.

From the results of these Examples and Comparative Examples, the effect of the surface structure (BET specific surface area and _{SBET- SCTAB} ) of the carrier defined in the present invention on the catalytic activity is clear.
Further, it is recognized that the definition of the present invention is also effective with respect to the loading amount of the macrocyclic compound complex of the transition metal and the loading amount of the noble metal (platinum). Further, as a method of preparing the catalyst, the effect of the heat treatment temperature after supporting the catalyst is clearly recognized, and the heat treatment within the temperature range specified in the present invention clearly improves the catalytic activity.

[0044]

[Table 1]

[0045]

As described above, the transition metal macrocyclic compound complex and the noble metal defined in the present invention are 500 m each.
^The amount of the noble metal supported by the catalyst composite-supported on the carbon material having a specific surface area of ² / g or more is about 1/7 as compared with the catalyst currently supporting 20% by mass of platinum which is normally used as standard. Nevertheless, at overvoltage, 4 electron reaction rate,
It exhibits almost the same catalytic activity, which brings about both reduction of catalyst cost and catalytic activity.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 5H018 AA06 AS03 BB01 BB06 BB08                       BB12 BB17 DD06 EE03 EE05                       EE08 EE11 EE16 EE17 HH02                       HH05 HH08                 5H026 AA06 BB01 EE05 EE11 EE17                       HH02 HH05 HH08

Claims (7)

[Claims] 1. A polymer solid electrolyte comprising a carbon material supporting a macrocyclic compound complex of a transition metal and a noble metal, wherein the carbon material has a BET specific surface area of 500 m ² / g or more. Type fuel cell oxygen electrode catalyst. 2. The carbon material is S _BET −S _CTAB ≧ 10.
The catalyst for polymer electrolyte fuel cell oxygen electrode according to claim 1, which satisfies 0 m ² / g. 3. The catalyst for a polymer solid oxide fuel cell oxygen electrode according to claim 1, wherein the cyclic structure of the macrocyclic compound is an N ₄ -chelate structure. 4. The catalyst for a polymer solid oxide fuel cell oxygen electrode according to claim 1, wherein the transition metal is Co and / or Fe. 5. The catalyst for polymer solid oxide fuel cell oxygen electrode according to claim 1, wherein the noble metal contained in the catalyst is 5% by mass or less. 6. The transition metal contained in the catalyst is 2% by mass.
The polymer solid oxide fuel cell oxygen electrode catalyst according to claim 1, wherein: 7. A carbon powder having a BET specific surface area of 500 m ² / g or more, the transition metal-containing macrocyclic compound and the noble metal being supported on the surface of the carbon powder, and then heat-treated at a temperature of 700 ° C. to 1100 ° C. A method for producing a catalyst for a polymer solid oxide fuel cell oxygen electrode.