JP2010084094A - Organometallic polymer structure, oxygen reduction catalyst and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organometallic polymer structure having improved oxygen-reduction activity compared with conventional polymer structures by increasing the amount of a coordinated metal in a metal-coordinated polymer. <P>SOLUTION: The organometallic polymer structure comprises: a polymer containing a π-conjugated system in the main chain; a counter ion introduced into the polymer, containing an anionic group having an organic skeleton, and expanding space between the polymer chains; and a metal coordinated to the polymer. The space between the polymer chains is expanded by the introduction of the counter ion. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a catalyst that promotes an oxygen reduction reaction in an aqueous solution, and more particularly to a catalyst used for an electrode of an electrochemical device such as a fuel cell and an air cell, and a structure, configuration, and manufacturing method of the electrode catalyst.

  A fuel cell or an air cell is an electrochemical energy device that uses oxygen in the air as an oxidant and extracts energy of a chemical reaction between the oxidant and a fuel compound or a negative electrode active material as electric energy.

  These batteries have higher theoretical energy capacity than secondary batteries such as lithium (Li) ion batteries, and should be used as in-vehicle power supplies, stationary distributed power supplies in homes and factories, or power supplies for portable electronic devices. Can do.

  On the oxygen electrode side of the fuel cell or air cell, an electrochemical reaction in which oxygen is reduced occurs.

  Oxygen reduction is a reaction that does not proceed easily at relatively low temperatures, and is generally promoted by a noble metal catalyst such as platinum (Pt), but it is still a major factor that limits the energy conversion efficiency of fuel cells and air cells. It has become one.

  Therefore, the realization of a catalyst that exhibits an oxygen reduction activity that exceeds the platinum fine particle catalyst is one of the major issues.

  As the oxygen reduction catalyst, a precious metal platinum (Pt) or an alloy thereof having fine particles having an average particle size of nanometer size supported on a carrier having a large specific surface area such as carbon black is used.

  Pt exhibits a relatively high oxygen reduction activity among known catalysts for electrochemical reactions that reduce oxygen to water, but it is still insufficient for practical use, and a large amount of Pt is required for use as a power source for the above applications. is necessary.

  Pt is rare and expensive, and using a large amount of Pt as an electrode catalyst has a practical problem in terms of cost. Therefore, the development of a catalyst that does not use platinum is considered as a major technical issue, such as increasing the specific surface area of platinum by further miniaturization or increasing the catalytic activity while reducing the amount of platinum by alloying.

  As a catalyst that does not use platinum, for example, a metal-based macrocyclic compound in which an atom / ionic metal is coordinated to an organic skeleton such as phthalocyanine or porphyrin is known (Non-patent Document 1).

  These catalysts can be coordinated with a relatively inexpensive metal other than platinum, and the amount of metal used is expected to be smaller than when a metal fine particle catalyst is used.

  However, the catalytic activity of most metal macrocycles is much lower than that of Pt. Furthermore, it is very unstable in an acidic solution and decomposes together with the oxygen reduction reaction, so that the fuel cell and the air cell cannot be operated stably for a long time.

  On the other hand, Patent Document 1 provides an oxygen reduction catalyst composed of a metal coordination polymer in which a metal is coordinated to a polymer, not a macrocyclic molecule such as porphyrin or phthalocyanine (Patent Document 1).

  In such a structure, high durability can be expected even in an acidic electrolyte by using a polymer resistant to acid. Further, since the metal is used in a monoatomic form, the amount of metal used and the cost can be greatly reduced.

  Furthermore, by using a polymer having an optimal structure, oxygen that is convenient for a four-electron reaction that can extract larger electric power than two oxygen reduction reaction paths of a two-electron reaction (formula 1) and a four-electron reaction (formula 2). A catalytic reaction site structure in which molecular bridge-type adsorption (Non-patent Document 2) occurs can be made to improve the oxygen reduction catalytic ability itself.

O ₂ + 2H ⁺ + 2e ⁻ → 2OH ⁻ (Formula 1)
O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O (Formula 2)

  On the other hand, in Non-Patent Document 3, a cobalt coordination polypyrrole having the highest activity as the metal coordination polymer described was prepared, and the atomic ratio between Co and N contained in the pyrrole ring was examined. It has been found that coordination is carried out only at a rate of about 1 per 20 atoms (Non-Patent Document 3).

JP 2005-66592 A R. Jasinski, “A New Fuel Cell Cathode Catalyst”, Nature, 201, 1964, p.1212 E. Yeager, “Electrocatalysts for O2 reduction”, Electrochim. Acta., 29, 1984, p. 1527, M. Yuasa, “Modifying Carbon Particles with Polypyrrole for Absorption of Cobalt Ions as Electrocatalystic Site for Oxygen Reduction”, Chem. Mater, 17, 2005, p4278

  As mentioned above, it is a metal coordination polymer that has high potential as an oxygen reduction catalyst, but the amount of coordination metal that is a catalytically active site is as low as several percent (atomic%) at most, and it is as high as platinum. There is a problem that catalytic activity is not obtained.

  In order to maximize the ability of the metal coordination polymer as a catalyst, it is necessary to further increase the amount of metal coordination.

  The present invention has been made in view of the above background, and its object is to increase the amount of coordination metal contained in the metal coordination polymer as compared with the conventional metalorganic polymer structure with improved oxygen reduction activity. The purpose is to provide.

  In order to achieve the above-described object, the first invention includes a polymer having a π-conjugated system in the main chain, an anion group introduced into the polymer and having an organic skeleton, and the spacing between the polymer chains being increased. An organometallic polymer structure comprising: a counter ion that expands; and a metal coordinated to the polymer.

  The second invention is an electrode catalyst in which the organometallic polymer structure described in the first invention is supported on an electrically conductive carrier.

  A third invention is a fuel cell using the organometallic polymer structure described in the first invention as an oxygen reduction catalyst.

  A fourth invention is an air battery using the organometallic polymer structure according to the first invention as an oxygen reduction catalyst.

  A fifth invention is a charge / discharge method characterized by using the fuel cell according to the third invention.

  A sixth invention is a charge / discharge method using the air battery according to the fourth invention.

  A seventh invention is characterized in that it has a step of introducing a counter ion containing an anionic group having an organic skeleton into a polymer containing a π-conjugated system in the main chain, and coordinating a metal to the polymer. It is a manufacturing method of a metal polymer structure.

  An eighth invention is a method for producing an electrocatalyst comprising a step of supporting the organometallic polymer structure according to the seventh invention on an electrically conductive carrier.

  According to a ninth aspect of the present invention, there is provided a fuel cell manufacturing method comprising a step of incorporating the organometallic polymer structure according to the seventh aspect of the invention as an oxygen reduction catalyst.

  A tenth aspect of the invention is a method for producing an air battery, comprising a step of incorporating the organometallic polymer structure according to the seventh aspect of the invention as an oxygen reduction catalyst.

  ADVANTAGE OF THE INVENTION According to this invention, the amount of coordination metals contained in a metal coordination polymer can be increased compared with the past, and the organometallic polymer structure which improved oxygen reduction activity can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

In the present invention, an anion having an organic skeleton, for example, a cyclic molecule and a counter ion containing an anion group, an alkyl group, an alkenyl group, or an alkynyl group (each having 2 to 16 carbon atoms) is used to reduce the spacing between polymer chains. Expanded to 3.5 to 5.5 mm (3.5 to 5.5 × 10 ⁻¹⁰ m), the metal arrangement has improved the amount of coordination metal by facilitating the penetration and diffusion of metal ions into the polymer. Coordination polymer and oxygen reduction catalyst are provided.

  Examples of organic anions constituting the counter ion include benzene and annulenes having different carbon numbers, naphthalene, anthracene, tetracene, pentacene and other acenes, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, At least one or more cyclic molecules such as helicene, coronene, and aromatic polycyclic compounds such as biphenyl, triphenylmethane, and acetoazilene can be used.

  As the anion group constituting the counter ion, carboxylic acid, sulfuric acid, sulfonic acid, sulfite anion, thiosulfate anion, carbonate anion, chromate anion, dichromate anion, monohydrogen phosphate anion, phosphate anion, etc. should be used. Can do.

  All or part of the hydrogen contained in the counter ion is converted into carbonyl group, amino group, imino group, cyano group, azo group, azo group, thiol group, sulfo group, nitro group, hydroxy group, acyl group, aldehyde group, cyclohexane Substitution with a substituent such as an alkyl group or an aryl group is also possible. By performing these substitutions, the hydrophilicity or hydrophobicity and shape of the counter ions can be adjusted to adjust the counter ion amount and the polymer chain spacing more finely.

  As the polymer for introducing the counter ion of the present invention, a polymer having a π-conjugated system in the structure can be used. Examples of the polymer having a π-conjugated system include polyacetylene, pyrrole, imidazole, pyrazole, tellurazole, isotellazole, selenazole, isoselenazole, thiozole, thiazole, isothiazole, oxazole, isoxazole, furazane, triazole, furan. , Dioxane, thiophene, selenophene, pyridine, pyrimidine, piperidine, pyrazine, piperazine, pyridazine, selenomorpholine, morpholine, pyran, dioxene, thiopyran, trithiane, thioxan, selenine, quinazoline, isoquinoline, quinoline, naphthyridine, acridine, benzoquinoline, phenanthroline , Quinoxaline, indole, indoline, indazole, carbazole, benzothiazole, benzimidazole, pyro Those containing at least one selected from pyridine, benzofuran, dihydrobenzofuran, phenoxathiin, dibenzofuran, dibenzodioxine, methylenedioxybenzene, benzoxazole, benzothiophene, dibenzothiophene, and thianthrene in the main chain and side chain It is done. The amount of counter ion introduced into the polymer can be determined by adjusting the amount of oxidation of the polymer. As a method for oxidizing the polymer, an electrochemical oxidation method, a chemical oxidation method using an oxidizing agent, or the like can be used.

  As the metal coordinated to the polymer whose distance between the chains is widened by the counter ion of the present invention, any transition metal or noble metal capable of acting as an oxygen adsorption site may be used. Among them, at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Zn, Ir, Pt, and Au is included. It is desirable to coordinate. A metal atom can be an adsorption site for oxygen molecules, and at the same time, an active site for dissociation and protonation of atomic oxygen.

  When used as an electrode catalyst for fuel cells or air cells, it may be dispersed or coated directly on the current collecting electrode, or dispersed on a carrier having a large specific surface area such as carbon fine particles, It may be applied. In order to reduce the amount of metal, it is desirable to support several layers of metal coordination polymer catalyst on a support having a large specific surface area. The support of the metal coordination polymer catalyst may be mixed at the time of synthesis of the catalyst, or may be mixed after the synthesis of the polymer catalyst. Further, when the supported catalyst is used as a catalyst electrode, an additive having ion conductivity such as a binder can be added. However, this catalyst loading method is not limited to the above, and any state may be used as long as the catalyst and the electrode are in electrical contact.

  An electrode catalyst including a metal coordination polymer catalyst can be used as an electrode catalyst for a fuel cell or an air cell.

  That is, a fuel cell and an air cell manufactured by incorporating the organometallic polymer structure according to the present embodiment as an oxygen reduction catalyst can also be used.

  As the fuel cell, an electrolytic solution having any property of an acidic solution, an alkaline solution, and a neutral solution can be used. The fuel of the fuel cell is not limited at all, and hydrogen or a hydrogen compound can be used. Similarly, in the case of an air battery, it can be used without being limited to an electrolytic solution or a negative electrode active material.

Hereinafter, details of the present invention will be specifically described in Examples. However, the present invention is not limited to these examples.

(Production of polypyrrole)
Polypyrrole (PPy) using p-dodecylbenzenesulfonic acid (DBS) having a dodecyl group at the para-position of benzenesulfonic acid as a counter ion, and iron (III) dodecylbenzenesulfonate shown below as an oxidizing agent were used. It was prepared by a chemical oxidative polymerization method.

  Iron (III) dodecylbenzenesulfonate was prepared by adding iron (III) chloride to a sodium dodecylbenzenesulfonate solution. The molar ratio of iron chloride to sodium dodecylbenzenesulfonate was 1: 3. If iron chloride is added and stirred, iron dodecylbenzenesulfonate will precipitate. The solution was centrifuged to remove the precipitate. Since there is a possibility that sodium chloride is mixed in the precipitate at this stage, it was thoroughly washed with ultrapure water and removed. After washing, sodium dodecylbenzenesulfonate was dissolved in methanol to obtain an oxidizing agent solution.

  Next, pyrrole monomer was added dropwise to ultrapure water and stirred to prepare pyrrole emulsified. An oxidizing agent was added dropwise thereto for chemical oxidative polymerization of pyrrole to obtain PPy-DBS containing dodecylbenzenesulfonic acid as a counter ion.

  As a comparative example, PPy-Cl was prepared using Cl described in Patent Document 1 as a counter ion.

(Measurement of polymer chain distance using XRD)
X-ray diffraction (XRD) measurement was performed on the three types of PPy produced, and the PPy chain spacing (d) was measured. As a result of analysis, in PPy-Cl, the average chain spacing was about 3.5 mm (3.5 × 10 ⁻¹⁰ m), whereas in PPy-DBS, the chain spacing was 5 mm (5 × 10 ⁻¹⁰ m). ) And a large value were obtained (FIG. 1). The value of 3.5 ｙ (3.5 × 10 ^-10 m) obtained in PPy-Cl is close to the graphene plane spacing of 3.46 Å (3.46 × 10 ^-10 m), and cyclic molecules were stacked. It is a general surface interval. If a counter ion having the characteristics of the present invention is used, this interval can be widened.

(Metal introduction)
Introducing cobalt, which is used as a coordination metal in Patent Document 1 or the like, into PPy was performed by the following method.

  Cobalt acetate was added to a methanol solution in which PPy was dispersed, and refluxing was performed for 6 hours in an inert gas atmosphere. After refluxing, it was thoroughly washed with ultrapure water, and the adsorbed cobalt was washed away without coordination to PPy. The washed sample was sufficiently dried to produce cobalt coordinated polypyrrole (CoPPy).

  The ratio of the amount of nitrogen derived from pyrrole and the amount of cobalt in CoPPy (standardized based on the atomic weight of nitrogen) was determined by organic elemental analysis and ICP emission spectroscopic analysis (Table 1).

  As a result of the measurement, it was found that PPy-DBS in which an increase in the PPy chain spacing was observed was coordinated with an amount of cobalt nearly twice that of PPy-Cl. The PPy chain spacing was increased by the counter ion, and it was possible to facilitate the penetration of cobalt into the PPy and improve the coordination amount of cobalt.

(Evaluation of PPy's ability to reduce oxygen)
The oxygen reduction ability of the produced Co-PPy was evaluated by the following method. In producing the electrode, first, ultrapure water was added to Co-PPy powdered in a mortar, and a dispersion was produced by ultrasonic irradiation. The dispersion was dripped and dried so that 10 μg of Co-PPy was supported on a 3 mm diameter glassy carbon (GC) electrode that had been well polished, and then 5 μl of a mixture of Nafion and propanol was dripped and dried to produce an electrode. Using the prepared electrode, the oxygen reduction activity was measured in an oxygen-saturated 1 M HClO ₄ aqueous solution.

  As a result of examining the oxygen reduction activity of three types of Co-PPy having different counter ions, the open circuit potential and the current value at 0.6 V were improved as the amount of introduced Co increased (FIG. 2). As a result of increasing the chain spacing of PPy by using counter ions to promote infiltration and diffusion of cobalt inside PPy and improving the amount of cobalt coordination, the oxygen reduction activity was improved.

(Introduction of substituents and effects of introduction)
PPy is prepared by using 2,1-dodecyl-sulfonic acid substituted with dodecyl group at the ortho position of the alkyl group of p-dodecylbenzenesulfonic acid as a counter ion, and then coordinating cobalt to the cobalt coordination amount. The influence of the substituents of was investigated.

The synthesis method of PPy and the synthesis method of cobalt were performed in the same manner as described in [Example 1] and [Example 3]. As a result of measuring the polymer chain interval by XRD, d = 5.3 cm (5.3 × 10 ⁻¹⁰ m) was obtained. Substitution of hydrogen in the benzene ring with a dodecyl group further increased the size of the counter ion and further expanded the polymer chain spacing. As a result of examining the coordination amount of cobalt by organic elemental analysis and ICP emission spectroscopic analysis, it was confirmed that the cobalt coordination amount was as high as 9%. By introducing a substituent and increasing the counter ion size, the polymer chain spacing could be further increased, and the cobalt coordination amount could be improved.

(Manufacture and characteristic evaluation of fuel cell electrode catalysts)
As shown in FIG. 3 (a), a fuel cell 1 using the metal coordination polymer structure of the present invention as a cathode electrode catalyst was produced, and its characteristics were evaluated.

  A small test fuel cell was produced according to the following procedure using the metal coordination polymer structure obtained by coordinating Co to PPy-DBS produced in [Example 1] as a catalyst for the cathode electrode. First, the diffusion layer 3 was prepared by applying carbon black water-repellent with a polytetrafluoroethylene (PTFE) dispersion on the surface of the carbon cloth and performing water-repellent treatment. Next, a powder of a metal coordination polymer structure in which Co was coordinated to PPy-DBS was applied as a catalyst 5 on the surface of the diffusion layer subjected to the water repellency treatment to form a cathode electrode 7. The anode electrode 13 was prepared by mixing a catalyst 11 supported on Pt on ketjen black as a diffusion layer 9 with a Nafion solution (polymer content 5% wt, manufactured by Aldrich) as a catalyst.

  Thereafter, the gas diffusion electrodes (cathode electrode 7 and anode electrode 13) are thermocompression-bonded from both surfaces of the electrolyte membrane 15 (a Nafion (registered trademark) membrane having a thickness of about 50 μm, manufactured by DuPont) with the catalysts 5 and 11 inside. A membrane electrode assembly (MEA) was obtained. Further, the MEA was sandwiched between current collectors 17 each having a gas flow path in a graphite plate to obtain a test battery.

FIG. 3B shows the results of a discharge test of the fuel cell 1 in which a metal coordination polymer structure in which Co is coordinated to PPy-DBS is used for the catalyst 5 of the cathode electrode. The test conditions are a cell temperature of 80 ° C., hydrogen and air pressure of 2.0 atm (2.0 × 10 ⁵ Pa), a hydrogen flow rate of 5 ml / s, an air flow rate of 9 ml / s, and a fuel gas temperature of hydrogen 80 ° C. and air 70 ° C. The catalytic activity of the cathode electrode 7 was high, and a high voltage was maintained even when the current density increased.

(Manufacture of electrode catalyst for air battery and characteristic evaluation)
As shown in FIG. 4 (a), a coin-type zinc-air battery (air battery 21) was prepared using Co-PPy-DBS as a catalyst for the cathode electrode, and its characteristics were evaluated.

  The manufacturing method is the same as that of a typical coin-type air battery. Separator 27 made of a porous resin film such as polypropylene or polyethylene is used for negative electrode can 23 (made of stainless steel coated with corrosion resistance coating) filled with zinc mixture 25 made of 40% potassium hydroxide gelled with zinc powder and starch. Sealed with. Next, a slurry obtained by kneading Ni-methylpyrrolidone solution in which Co-PPy-DBS powder, carbon black, and polyvinylidene fluoride prepared in [Example 1] and [Example 3] were applied was applied to a nickel wire mesh. The positive electrode catalyst layer 29 and the microporous Teflon (registered trademark) film 31 were attached to the outside of the separator 27. Thereafter, two positive electrode cans 35 each provided with an air inlet hole 33 with a plastic insulating gasket 37 are attached to the negative electrode can 23 to which the separator 27, the positive electrode catalyst layer 29, and the microporous Teflon (registered trademark) film 31 are attached. Sealed in a state where the gap was insulated.

  The result of the discharge test at room temperature of the manufactured coin-type air battery 21 is shown in FIG. A flat discharge curve was recorded at a high voltage of 1.15V. Therefore, it is considered that the metal coordination polymer structure of the present invention is also effective as a cathode electrode catalyst for an air battery.

(Other polymer components, ligands, metals, etc.)
Cobalt coordinated polypyrrole was synthesized using other cyclic molecules not described in Examples 1 to 7, an alkyl group having a different carbon number, and a dopant containing a sulfonate anion, and their polymer chain spacing and coordinated metal content. Evaluated. The synthesis method was the same as that described in Examples 1 and 3. The polymer chain spacing (d) was determined by XRD, and the amount of coordination metal was examined by component analysis and ICP emission spectroscopic analysis. Table 2 shows the results obtained. In the figure,% is atomic%.

  Cobalt coordinated polypyrrole was synthesized using a dodecyl group, a sulfonate anion, and a meta group of a sulfonate group of a dopant containing a cyclic molecule substituted with various substituents, and their polymer chain spacing and coordination metal content. Evaluated. The synthesis method is the same as that described in Examples 1 and 3. The polymer chain spacing (d) was determined by XRD, and the amount of coordination metal was examined by component analysis and ICP emission spectroscopic analysis. Table 3 shows the results obtained. In the figure,% is atomic%.

  As is clear from the above results, by using the oxygen reduction catalyst comprising the metal coordination polymer structure according to the present embodiment, a catalyst having excellent stability and high activity and capable of reducing the amount of metal is provided. can do.

  In the above-described embodiments and examples, the case where the organometallic polymer structure is applied to the fuel cell 1 and the air cell 21 has been described. However, the present invention is not limited to this, and metal is conventionally used. It can be applied to all organometallic polymer structures that need to be supported more.

It is a figure which shows the result of having measured the space | interval of PPy chain | strand using X-ray diffraction (XRD). It is a figure which shows the oxygen reduction activity of CoPPy. FIG. 3A is a cross-sectional view showing the fuel cell 1, and FIG. 3B is a diagram showing the result of a discharge test of the fuel cell 1. FIG. 4A is a cross-sectional view showing the air battery 21, and FIG. 4B is a view showing a result of a discharge test of the air battery 21.

Explanation of symbols

1 ………… Fuel cell 3 ………… Diffusion layer 5 ………… Catalyst 7 ………… Cathode electrode 9 ………… Diffusion layer 11 ………… Catalyst 13 ……… Anode electrode 15 ……… Electrolyte Membrane 17 ......... Current collector 21 ......... Air battery 23 ......... Negative electrode can 25 ......... Zinc composite 27 ......... Separator 29 ......... Positive catalyst layer 31 ......... Microporous Teflon (registered trademark) ) Film 33 ……… Air inlet 35 ……… Positive can 37 ……… Gasket

Claims (26)

a polymer containing a π-conjugated system in the main chain;
A counter ion introduced into the polymer, including an anionic group having an organic skeleton, and extending a distance between the polymer chains;
A metal coordinated to the polymer;
An organometallic polymer structure characterized by comprising: The organometallic polymer structure according to claim 1, wherein an interval between the polymer chains is 3.5 to 5.5 mm (3.5 to 5.5 × 10 ⁻¹⁰ m). The metal is
Having at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Zn, Ir, Pt, Au The organometallic polymer structure according to claim 1, wherein: The polymer is
As the main chain or part of the main chain, polyacetylene, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, biphenyl, triphenylmethane, aceto Preazilene, pyrrole, imidazole, pyrazole, tellurazole, isotelrazole, selenazole, isoselenazole, thiozole, thiazole, isothiazole, oxazole, isoxazole, furazane, triazole, furan, dioxane, thiophene, selenophene, pyridine, pyrimidine, Piperidine, pyrazine, piperazine, pyridazine, selenomorpholine, morpholine, pyran, dioxene, thiopyran, trithiane, thioxa , Selenine, quinazoline, isoquinoline, quinoline, naphthyridine, acridine, benzoquinoline, phenanthroline, quinoxaline, indole, indoline, indazole, carbazole, benzothiazole, benzimidazole, pyrrolopyridine, benzofuran, dihydrobenzofuran, phenoxathiin, dibenzofuran, dibenzodioxin 4. The organometallic polymer structure according to claim 1, comprising at least one selected from the group consisting of benzene, methylenedioxybenzene, benzoxazole, benzothiophene, dibenzothiophene, and thianthrene. The polymer is
As the side chain or part of the side chain, polyacetylene, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, biphenyl, triphenylmethane, aceto Preazilene, pyrrole, imidazole, pyrazole, tellurazole, isotelrazole, selenazole, isoselenazole, thiozole, thiazole, isothiazole, oxazole, isoxazole, furazane, triazole, furan, dioxane, thiophene, selenophene, pyridine, pyrimidine, Piperidine, pyrazine, piperazine, pyridazine, selenomorpholine, morpholine, pyran, dioxene, thiopyran, trithiane, thioxa , Selenine, quinazoline, isoquinoline, quinoline, naphthyridine, acridine, benzoquinoline, phenanthroline, quinoxaline, indole, indoline, indazole, carbazole, benzothiazole, benzimidazole, pyrrolopyridine, benzofuran, dihydrobenzofuran, phenoxathiin, dibenzofuran, dibenzodioxin 5. The organometallic polymer structure according to claim 1, comprising at least one selected from the group consisting of benzene, methylenedioxybenzene, benzoxazole, benzothiophene, dibenzothiophene, and thianthrene. The counter ion is
Benzene and annulenes with different carbon numbers, naphthalene, anthracene, tetracene, pentacene and other acenes, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, aromatic polycyclic compounds The organometallic polymer structure according to any one of claims 1 to 5, comprising at least one of certain biphenyls, triphenylmethanes, acepleazilenes and derivatives of the organic compounds. The counter ion is
The organometallic polymer structure according to any one of claims 1 to 6, comprising at least one of an alkyl group, an alkenyl group, and an alkynyl group. The counter ion is
Containing at least one or more selected from carboxylate anion, sulfate anion, sulfonate anion, sulfite anion, thiosulfate anion, carbonate anion, chromate anion, dichromate anion, monohydrogen phosphate anion, phosphate anion The organometallic polymer structure according to any one of claims 1 to 7, wherein   All or part of the hydrogen contained in the counter ion is carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, nitro group, hydroxy group, acyl group, aldehyde group, cyclohexane The organometallic polymer structure according to any one of claims 1 to 8, which is substituted with at least one selected from substituents such as an alkyl group and an aryl group.   An electrode catalyst comprising the organometallic polymer structure according to claim 1 supported on an electrically conductive carrier.   A fuel cell using the organometallic polymer structure according to claim 1 as an oxygen reduction catalyst.   An air battery using the organometallic polymer structure according to claim 1 as an oxygen reduction catalyst.   A charge / discharge method using the fuel cell according to claim 11.   A charge / discharge method using the air battery according to claim 12.   An organometallic polymer structure comprising a step of introducing a counter ion containing an anionic group having an organic skeleton into a polymer containing a π-conjugated system in the main chain, and coordinating a metal to the polymer. Production method. The process includes
Introducing the counter ion into the polymer has a step of setting the distance between the polymer chains to 3.5 to 5.5 mm (3.5 to 5.5 × 10 ⁻¹⁰ m). The method for producing an organometallic polymer structure according to claim 15. The process includes
The metal is at least one selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Zn, Ir, Pt, and Au. The method for producing an organometallic polymer structure according to claim 15, further comprising a step of coordinating a metal. The polymer is
As the main chain or part of the main chain, polyacetylene, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, biphenyl, triphenylmethane, aceto Preazilene, pyrrole, imidazole, pyrazole, tellurazole, isotelrazole, selenazole, isoselenazole, thiozole, thiazole, isothiazole, oxazole, isoxazole, furazane, triazole, furan, dioxane, thiophene, selenophene, pyridine, pyrimidine, Piperidine, pyrazine, piperazine, pyridazine, selenomorpholine, morpholine, pyran, dioxene, thiopyran, trithiane, thioxa , Selenine, quinazoline, isoquinoline, quinoline, naphthyridine, acridine, benzoquinoline, phenanthroline, quinoxaline, indole, indoline, indazole, carbazole, benzothiazole, benzimidazole, pyrrolopyridine, benzofuran, dihydrobenzofuran, phenoxathiin, dibenzofuran, dibenzodioxin The production of an organometallic polymer structure according to any one of claims 15 to 17, comprising at least one selected from the group consisting of benzene, methylenedioxybenzene, benzoxazole, benzothiophene, dibenzothiophene, and thianthrene. Method. The polymer is
As the side chain or part of the side chain, polyacetylene, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, biphenyl, triphenylmethane, aceto Preazilene, pyrrole, imidazole, pyrazole, tellurazole, isotelrazole, selenazole, isoselenazole, thiozole, thiazole, isothiazole, oxazole, isoxazole, furazane, triazole, furan, dioxane, thiophene, selenophene, pyridine, pyrimidine, Piperidine, pyrazine, piperazine, pyridazine, selenomorpholine, morpholine, pyran, dioxene, thiopyran, trithiane, thioxa , Selenine, quinazoline, isoquinoline, quinoline, naphthyridine, acridine, benzoquinoline, phenanthroline, quinoxaline, indole, indoline, indazole, carbazole, benzothiazole, benzimidazole, pyrrolopyridine, benzofuran, dihydrobenzofuran, phenoxathiin, dibenzofuran, dibenzodioxin The production of an organometallic polymer structure according to any one of claims 15 to 18, comprising at least one selected from the group consisting of methylenedioxybenzene, benzoxazole, benzothiophene, dibenzothiophene, and thianthrene. Method. The counter ion is
Benzene and annulenes with different carbon numbers, naphthalene, anthracene, tetracene, pentacene and other acenes, phenanthrene, chrysene, triphenylene, tetraphen, pyrene, picene, pentaphen, perylene, helicene, coronene, aromatic polycyclic compounds 20. The production of an organometallic polymer structure according to any one of claims 15 to 19, comprising at least one of certain biphenyls, triphenylmethanes, acepleazilenes and derivatives of the organic compounds. Method. The counter ion is
The method for producing an organometallic polymer structure according to any one of claims 15 to 20, comprising at least one of an alkyl group, an alkenyl group, and an alkynyl group. The counter ion is
Containing at least one or more selected from carboxylate anion, sulfate anion, sulfonate anion, sulfite anion, thiosulfate anion, carbonate anion, chromate anion, dichromate anion, monohydrogen phosphate anion, phosphate anion The method for producing an organometallic polymer structure according to any one of claims 15 to 21.   All or part of the hydrogen contained in the counter ion is carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, nitro group, hydroxy group, acyl group, aldehyde group, cyclohexane The method for producing an organometallic polymer structure according to any one of claims 15 to 22, which is substituted with at least one selected from substituents such as an alkyl group and an aryl group.   24. A process for producing an electrode catalyst, comprising a step of supporting the organometallic polymer structure according to claim 15 on an electrically conductive carrier.   A method for producing a fuel cell, comprising the step of incorporating the organometallic polymer structure according to claim 15 as an oxygen reduction catalyst.   24. A method for producing an air battery, comprising the step of incorporating the organometallic polymer structure according to claim 15 as an oxygen reduction catalyst.

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