WO2016035321A1 - 共有結合性有機構造体を含む導電性ハイブリッド材料 - Google Patents
共有結合性有機構造体を含む導電性ハイブリッド材料 Download PDFInfo
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- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H01M4/9041—Metals or alloys
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a conductive hybrid material containing a covalently bonded organic structure. Specifically, the present invention relates to a conductive hybrid material including a covalently bonded organic structure that can be suitably used as a catalyst material or an electrode material.
- the hydrogen oxidation reaction is important in the anode reaction of an H 2 / O 2 fuel cell.
- a hydrogen generation reaction that is the reverse reaction of the hydrogen oxidation reaction is important in the cathode reaction of an electrolytic cell.
- platinum group elements such as platinum, palladium and iridium and platinum group element compounds such as platinum ruthenium alloys are widely used as catalysts. .
- Patent Document 1 discloses using a catalyst in which platinum particles are supported on a carrier such as carbon black powder on the fuel electrode side of a solid polymer fuel cell as a hydrogen oxidation catalyst.
- Patent Document 2 discloses that a thin film obtained by forming a platinum film on indium tin oxide (ITO) by a sputtering method is disclosed as a hydrogen generation catalyst.
- Patent Document 2 discloses that the hydrogen generation overvoltage of platinum and a nanostructure containing platinum is small.
- Patent Document 3 discloses that nickel oxide powder is plasma sprayed on the surface of a nickel expanded metal substrate and the substrate is coated with nickel oxide powder as a catalyst for the hydrogen generation reaction.
- a covalent organic structure is a porous crystalline polymer having meso and micro-sized pores, and is known to be synthesized by a polycondensation reaction such as boronic acid (for example, Patent Document 4 and Non-patent document 1).
- the covalent organic structure is a substance that can achieve both high durability by being constructed with only covalent bonds and high design flexibility due to the wide selection of frameworks.
- utilization in applications such as gas adsorption / separation has been studied by utilizing the property of being porous, but functional porous materials such as next-generation catalysts or catalyst carriers have been studied from the above characteristics. The application as is also attracting attention.
- the nickel compound of Patent Document 3 has a hydrogen oxidation / hydrogen generation overvoltage of 100 mV or more with respect to platinum, and has a problem that energy is consumed much more than platinum in the reaction.
- the platinum group elements of Patent Documents 1 and 2 are expensive although the hydrogen oxidation / hydrogen generation overvoltage is extremely small, the platinum group element is supported by supporting the conductive porous carrier as nanoparticles of 3 to 20 nm. It has been used with improved surface area. However, even in such a case, in order to obtain a sufficient current density, it is necessary to increase the amount of the metal supported, which causes a problem of high cost.
- the covalently bonded organic structure itself has poor electronic conductivity. Therefore, so far, it has been difficult to use as an electrode catalyst, a catalyst material accompanied by an electron transfer reaction, an electrode material of a secondary battery, and the like.
- An object of the present invention is to provide a novel conductive material.
- Another object of the present invention is to provide a conductive material having high catalytic activity even when the amount of supported metal is reduced.
- the conductive hybrid material according to the first aspect of the present invention includes a covalent organic structure having a pore and a conductive material, and the covalent organic structure is on the conductive material. It is carried on.
- the electrode according to the second aspect of the present invention includes a conductive hybrid material that includes a covalent organic structure having a pore and a conductive material, and the covalent organic structure is supported on the conductive material. To do.
- the catalyst according to the third aspect of the present invention includes a conductive hybrid material including a covalent organic structure having pores and a conductive material, and the covalent organic structure is supported on the conductive material. To do.
- the hydrogen generation catalyst according to the fourth aspect of the present invention includes a conductive hybrid material including a covalent organic structure having a pore and a conductive material, and the covalent organic structure is supported on the conductive material. Having a catalyst containing A platinum group element is coordinated to the covalently bonded organic structure.
- the hydrogen oxidation catalyst according to the fifth aspect of the present invention includes a conductive hybrid material including a covalent organic structure having a pore and a conductive material, and the covalent organic structure is supported on the conductive material. Having a catalyst containing A platinum group element is coordinated to the covalently bonded organic structure.
- the oxygen reduction catalyst according to the sixth aspect of the present invention includes a conductive hybrid material including a covalent organic structure having pores and a conductive material, and the covalent organic structure is supported on the conductive material. Having a catalyst containing The conductor material is a carbon material.
- FIG. 1 shows a scanning electron microscope image of a conductive hybrid material according to an embodiment of the present invention.
- FIG. 2 is a graph showing an oxygen reduction potential-current curve of the conductive hybrid material (Pt / CTF-1 / KB) according to the embodiment of the present invention.
- FIG. 3 is a graph showing a comparison between the oxygen reduction potential-current curve of the covalently bonded organic structure and the oxygen reduction potential-current curve of the conductive hybrid material.
- FIG. 4 is a graph showing oxygen reduction potential-current curves of the conductive hybrid material (Pt / CTF-1 / KB) and the material of Comparative Example 1 (20 mass% Pt / C) in the presence of methanol and oxygen. It is.
- FIG. 1 shows a scanning electron microscope image of a conductive hybrid material according to an embodiment of the present invention.
- FIG. 2 is a graph showing an oxygen reduction potential-current curve of the conductive hybrid material (Pt / CTF-1 / KB) according to the embodiment of the present invention
- FIG. 5 shows an oxygen reduction potential-current curve of the conductive hybrid material (Pt / CTF-1 / KB) and the material of Comparative Example 1 (20 mass% Pt / C) when methanol is present but oxygen is not present. It is a graph which shows.
- FIG. 6 is a graph showing an oxygen reduction potential-current curve of the conductive hybrid material (Cu / CTF-1 / KB) according to the embodiment of the present invention.
- FIG. 7 is a graph showing oxygen reduction potential-current curves of conductive hybrid materials (Cu / CTF-3 / KB, Cu / CTF-5 / KB and Cu / CTF-6 / KB) according to an embodiment of the present invention. It is.
- FIG. 1 shows an oxygen reduction potential-current curve of the conductive hybrid material (Pt / CTF-1 / KB) and the material of Comparative Example 1 (20 mass% Pt / C) when methanol is present but oxygen is not present. It is a graph which shows.
- FIG. 6 is
- FIG. 8 is a graph showing an oxygen reduction potential-current curve of a conductive hybrid material (Pt / CTF-1 / KB, Cu / CTF-7 / KB) according to an embodiment of the present invention.
- FIG. 9 is a graph showing the results of linear sweep voltammetry performed on the hybrid materials of Examples 2-1 to 2-7 and the material of Comparative Example 2.
- FIG. 10 is a graph showing the results of linear sweep voltammetry performed on the hybrid materials of Examples 2-1 to 2-7 and the material of Comparative Example 2.
- FIG. 11 is a graph showing the relationship between the elemental composition ratio and the current density in the hydrogen oxidation reaction per unit platinum amount in the hybrid materials of Examples 2-1 to 2-7 and the material of Comparative Example 2.
- FIG. 12 is a graph showing the relationship between the elemental composition ratio and the current density in the hydrogen generation reaction per unit platinum amount in the hybrid materials of Examples 2-1 to 2-7 and the material of Comparative Example 2.
- the conductive hybrid material of this embodiment includes a covalent organic structure having pores and a conductive material, and the covalent organic structure is supported on the conductive material. .
- the “covalent organic structure” is a molecule formed by connecting atoms such as hydrogen, carbon, nitrogen, oxygen, boron, and sulfur only by a covalent bond. More specifically, the covalent bond organic structure means a polymer having a structure in which a plurality of the same or different aromatic ring groups form a cyclic repeating unit by a covalent bond.
- the covalently bonded organic structure also means a polymer having a two-dimensional or three-dimensional network structure in which the repeating unit is continuously connected to one or more other repeating units by a covalent bond.
- Such a covalently bonded organic structure has a porous structure having meso and micro-sized pores, and has a low density and excellent thermal stability.
- the covalently bonded organic structure used for the conductive hybrid material of the present embodiment is preferably a polymer composed of repeating units having a plurality of triazine rings in the molecule. As described above, the repeating unit is connected to another adjacent repeating unit by a covalent bond, and a structure is formed by repeating such a structure in a chain manner.
- the covalent organic structure has a structure in which a plurality of triazine rings are covalently linked via an arylene, heteroarylene, or heteroatom.
- arylene means a divalent functional group obtained by removing two hydrogen atoms bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon.
- Heteroarylene means a divalent functional group formed by removing two hydrogen atoms from a heterocyclic compound having aromaticity.
- the arylene is phenylene.
- the heteroarylene is pyridylene.
- the arylene and heteroarylene may have a substituent, and such a substituent is not particularly limited, and may be, for example, alkyl or halogen.
- a hetero atom sulfur, boron, nitrogen, phosphorus, etc. can be mentioned, Preferably it is sulfur or nitrogen.
- a covalent organic structure having a triazine ring can be obtained as follows. First, a triazine ring is formed by subjecting a monomer having a dicyano group or a tricyano group to a condensation reaction. Next, by repeating the condensation reaction, a covalent organic structure in which a plurality of triazine rings are finally connected by a covalent bond can be obtained. In obtaining the conductive hybrid material in the present embodiment, the condensation reaction can be preferably performed in-situ on the conductor material.
- the monomer having a dicyano group is preferably dicyanobenzene or dicyanopyridine.
- the monomer having a tricyano group is preferably tricyanobenzene or tricyanopyridine.
- the monomer is dicyanobenzene, a structure in which a plurality of triazine rings are connected via a phenylene as described above via a phenylene bond.
- the monomer is dicyanopyridine, a structure in which a plurality of triazine rings are linked by a covalent bond via pyridylene as described above. Therefore, the covalently bonded organic structure preferably has a structure in which a plurality of triazine rings are connected by covalent bonds via phenylene or pyridylene.
- the covalent organic structure is preferably a compound obtained by a condensation reaction of dicyanobenzene or dicyanopyridine.
- the monomer having a dicyano group can further have a substituent.
- a substituent is not particularly limited as long as the condensation reaction of the cyano group proceeds, and can be, for example, an alkyl group or a halogen group.
- the covalently bonded organic structure used for the conductive hybrid material of the present embodiment preferably has 1 nm to 50 nm pores. Also preferably, the covalently bonded organic structure has a molecular weight in the range of 1000-20000.
- a metal is coordinated to the covalently bonded organic structure. That is, it is preferable that the covalent organic structure is modified with a metal by a coordinate bond.
- a metal can be a transition metal, preferably a platinum group element or copper.
- the platinum group element is preferably at least one selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum.
- the metal can exist in a complex form with the covalent organic structure by forming a coordination bond with the heteroatom of the heteroaromatic ring constituting the covalent organic structure. And by coordinating a metal to a covalent bond organic structure, a metal can be disperse
- a typical example of the covalently bonded organic structure used in the conductive hybrid material of the present embodiment is a compound having a structure represented by the following chemical formula 1.
- the compound of Chemical Formula 1 can be synthesized by forming a triazine ring by condensation reaction of 2,6-dicyanopyridine and repeating the reaction, as shown in the examples described later.
- the compound has a structure in which triazine rings are linked by a covalent bond via a pyridylene group.
- a repeating unit having a cyclic structure composed of three triazine rings and three pyridine rings is formed, and the plurality of repeating units are further linked by a pyridylene group.
- the compound of Chemical Formula 1 is a polymer having a plurality of pores and a two-dimensional network structure.
- the covalently bonded organic structure containing the triazine ring of Formula 1 is sometimes referred to as CTF (Covalent Triazine Framework) in particular.
- the metal can be supported on the covalently bonded organic structure. That is, for example, as shown in Chemical Formula 2, a complex can be formed by forming a coordinate bond between a nitrogen atom of a triazine ring or a nitrogen atom of a pyridylene group and a metal.
- covalently bonded organic structure used in the conductive hybrid material of the present embodiment are not limited to these, but preferably include the following compounds.
- examples of the covalently bonded organic structure according to this embodiment include a compound containing a porphyrin ring represented by Chemical Formula 4.
- the covalently bonded organic structure of Chemical Formula 4 can be synthesized by the method described in X. Feng et al., Chem. Commun., 2011, 47, 1979-1981.
- a metal can be supported on the covalently bonded organic structure represented by Chemical Formula 4. That is, a complex can be formed by forming a coordinate bond between the nitrogen atom of the porphyrin ring and the metal.
- Examples of the covalently bonded organic structure according to this embodiment include a compound containing a porphyrin ring and a phthalocyanine ring represented by Chemical Formula 5.
- the covalently bonded organic structure of Chemical Formula 5 can be synthesized by the method described in Venkata S. Pavan K. Neti et al. CrystEngComm, 2013, 15, 6892-6895.
- a metal can also be supported on the covalently bonded organic structure represented by Chemical Formula 5. That is, a complex can be formed by forming a coordinate bond between the nitrogen atom of the porphyrin ring and the phthalocyanine ring and the metal.
- Examples of the covalently bonded organic structure according to this embodiment include a cyclic compound represented by Chemical Formula 7 in which a three-dimensional compound represented by Chemical Formula 6 is bonded via a 4,4′-biphenylene group.
- the compounds of Chemical Formula 6 and Chemical Formula 7 can be synthesized by the method described in Y.-B. Zhang et al., J. Am. Chem. Soc. 2013, 135, 16336-16339.
- examples of the covalently bonded organic structure according to this embodiment include a cyclic compound represented by Chemical Formula 9 in which a three-dimensional compound represented by Chemical Formula 8 is bonded.
- the compounds of Chemical Formula 8 and Chemical Formula 9 can be synthesized by the method described in Q. Fang et al., J. Am. Chem. Soc. 2015, 137, 8352-8355.
- the conductive material used together with the covalently bonded organic structure can be generally used as a conductive material for an electrode of a secondary battery in the technical field.
- the conductor material is not particularly limited as long as it can impart electronic conductivity to the covalent organic structure by supporting the covalent organic structure.
- the conductor material is preferably a carbon material.
- the carbon material constituting the conductive material at least one selected from the group consisting of graphite, carbon black, ketjen black, acetylene black, carbon nanotube, graphene, and carbon fiber can be used.
- amorphous carbon can also be used as a carbon material which comprises a conductor material. Since these carbon materials are excellent in conductivity and corrosion resistance, high electrode performance can be maintained for a long period of time when the conductive hybrid material is used for an electrode or the like.
- the carbon material constituting the conductor material is preferably in the form of nanoparticles. That is, the carbon material preferably has a particle size of 10 nm to 300 nm. When the particle size of the carbon material is within this range, the covalent bond organic structure and the metal coordinated to the covalent bond organic structure can be highly dispersed, and the activity of the metal can be increased. Become.
- the particle size of the carbon material can be determined by observing the conductive hybrid material with a scanning electron microscope (SEM), for example.
- the ratio of the covalently bonded organic structure and the conductive material is preferably 100: 10 or more in terms of the mass ratio of the covalently bonded organic structure: conductive material. Further, it is more preferable that the covalent bond organic structure: conductor material is 100: 20 to 100: 5000 by mass ratio.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material is preferably 0.005 to 1. That is, the ratio of the total number of atoms of the elements constituting the covalent bond organic structure to the total number of atoms of the elements constituting the conductor material ([total number of atoms of the elements constituting the covalent bond organic structure] / [conductor The total number of atoms of the elements constituting the material]) is preferably 0.005 to 1.
- the composition ratio between the covalently bonded organic structure and the conductor material is within this range, the covalently bonded organic structure is easily supported on the surface of the conductor material with a certain film thickness.
- the element composition ratio in the present embodiment is a value obtained by performing a narrow scan of X-ray photoelectron spectrum analysis (XPS) on each element constituting the conductive hybrid material and quantifying the peak area.
- XPS X-ray photoelectron spectrum analysis
- a value measured using monochromatic Al X-ray (10 kV) is used for the excitation X-ray.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material is 0.005 to 0.60. It is preferably 0.05 to 0.50.
- the covalently bonded organic structure is preferably a compound obtained by an in-situ reaction in which a monomer is polymerized on a conductive material.
- the monomer is subjected to a condensation reaction in a molten salt such as ZnCl 2 in a state where the carbon material nanoparticles are mixed with the monomer of the covalently bonded organic structure.
- the formation reaction of a covalent organic structure can be performed in-situ on the conductor material.
- the monomer of the covalently bonded organic structure include dicyanobenzene, dicyanopyridine, tricyanobenzene, and tricyanopyridine as described above.
- the conductive hybrid material of the present embodiment can impart electronic conductivity by supporting a covalently bonded organic structure on a conductive material such as a carbon material, and further highly disperse metal at an atomic level. Can be made. Therefore, the conductive hybrid material can be used as an electrode catalyst in secondary batteries and fuel cells known in the art, or as a catalyst or electrode in other systems involving electron transfer.
- the electrode according to the present embodiment includes a conductive hybrid material including a covalent organic structure having a pore and a conductive material, and the covalent organic structure is supported on the conductive material. It is preferable to contain. Moreover, it is preferable that the catalyst which concerns on this embodiment also contains the said electroconductive hybrid material.
- the binder used for binding the catalyst to the base material.
- the binder include Nafion (manufactured by DuPont), Flemion (registered trademark) (manufactured by Asahi Glass Co., Ltd.), Aciplex (registered trademark) (Asahi Kasei E).
- Cation exchange resins such as Materials Co., Ltd., anion exchange resins such as AS-4 (Tokuyama Co., Ltd.), fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), styrene
- fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
- PVDF polyvinylidene fluoride
- styrene examples thereof include latex materials such as butadiene rubber (SBR), and polymer materials such as polyacrylic acid, polyvinyl alcohol, and polyacrylamide. These polymer materials may be used alone or in combination of two or more.
- the binder is not particularly limited as long as it has a binding function.
- a conductive hybrid material as an electrode catalyst
- materials known in the technical field can be used as the active material and binder in the electrode depending on the type of battery and the like used.
- a method commonly used in the technical field can be used as a method for manufacturing the electrode.
- the conductive hybrid material of the present embodiment is particularly suitable as an electrode material or the like in a fuel cell or the like using methanol because it selectively reacts with oxygen even in the presence of methanol and hardly exhibits a reaction activity with respect to methanol.
- a conductive support agent when using the said conductive hybrid material for an electrode etc., you may add a conductive support agent.
- conductive carbon is mainly used.
- the conductive carbon for example, carbon black, fiber-like carbon, graphite and the like are preferably used.
- the conductive hybrid material of this embodiment can highly disperse platinum group elements at the atomic level. Therefore, the conductive hybrid material can be suitably used as a hydrogen generation catalyst, a hydrogen oxidation catalyst, and an oxygen reduction catalyst.
- the hydrogen generation catalyst and the hydrogen oxidation catalyst of this embodiment include a covalently bonded organic structure having a pore and a conductive material, and the covalently bonded organic structure is supported on the conductive material. It has a catalyst containing a conductive hybrid material. And it is preferable that the platinum group element is coordinated to the said covalent bond organic structure.
- the oxygen reduction catalyst according to the present embodiment includes a conductive organic material including a covalent organic structure having a pore and a conductive material, and the covalent organic structure is supported on the conductive material. It has a catalyst to do. And it is preferable that the said conductor material is a carbon material.
- the conductive hybrid material of the present embodiment is not limited to use as an electrode material or the like.
- the conductive hybrid material of the present embodiment is useful as a material for purifying soil contaminated with heavy metals and a material for recovering rare metals by utilizing the feature that the conductive hybrid material forms a coordination bond with the metal and retains the metal. It is.
- the metal forms a complex with the covalent organic structure by forming a coordination bond with a heteroatom of the heteroaromatic ring constituting the covalent organic structure.
- the conductive hybrid material is useful as a complex catalyst in an organic synthesis reaction. Moreover, it can be used as an asymmetric synthesis catalyst by imparting chirality to the structure of the covalently bonded organic structure.
- the conductive hybrid material of the present embodiment has an advantage that the catalyst can be easily recovered when used in an organic synthesis reaction since the complex structure is supported on the support.
- Example 1-1 Synthesis of Conductive Hybrid Material According to the scheme shown in Chemical Formula 10, a hybrid material carrying a platinum complex of a covalently bound triazine structure (CTF-1) on Ketjen Black (KB) was synthesized.
- CTF-1 covalently bound triazine structure
- KB Ketjen Black
- the resulting mixture was then sealed in a glass tube and heated under vacuum conditions. The mixture was then maintained at a temperature of 400 ° C. for 21 hours.
- the obtained powder was washed with 0.1 M HCl, water, tetrahydrofuran (THF), and acetonitrile, and then dried under reduced pressure.
- the powder after drying was impregnated with an aqueous solution of K 2 [PtCl 4 ] (manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 160 mM at 60 ° C. for 4 hours to add platinum. Thereafter, it was washed with water and acetone and then dried to obtain a hybrid material (Pt / CTF-1 / KB).
- a hybrid material (Pt / CTF-1 / KB) in which the mass ratio of platinum / CTF: Ketjenblack was 100: 5, 100: 20, 100: 100 was also prepared by the same production method as described above.
- Pt / CTF-1 indicates a compound in which a platinum complex is supported on a covalently bonded triazine structure (CTF-1).
- Pt / CTF-1 / KB indicates a hybrid material in which the above-described Pt / CTF-1 is supported on ketjen black.
- Example 1-2 First, as in Example 1, 1.363 g ZnCl 2 , 0.129 g 2,6-dicyanopyridine, and 0.129 g ketjen black were mixed in a glove box.
- the resulting mixture was then sealed in a glass tube and heated under vacuum conditions. The mixture was then maintained at a temperature of 400 ° C. for 21 hours.
- the obtained powder was washed with 0.1 M HCl, water, tetrahydrofuran, and acetonitrile, and then dried under reduced pressure. Then, the dried powder was impregnated with an aqueous solution of CuCl 2 (manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 160 mM at 60 ° C. for 4 hours to add copper. Thereafter, the powder was washed with water, further mixed with 0.1 M NaOH aqueous solution, and then stirred for 1 hour while irradiating ultrasonic waves.
- Cu / CTF-1 / KB indicates a hybrid material in which a copper complex of a covalently bonded triazine structure (CTF-1) is supported on ketjen black.
- Chemical formula 11 shows the partial structure of only the repeating unit.
- Example 1-3 CTF-2, CTF-4 and CTF-5 having the following structures were respectively obtained in the same manner as in Example 1-1 except that the dicyanobenzene derivative represented by Chemical Formula 12 was used instead of 2,6-dicyanopyridine. A hybrid material retained with ketjen black was synthesized.
- the upper part of Chemical Formula 12 shows the structure of the monomer used, and the lower part shows the structure of CTF.
- CTF-3 was synthesized almost according to the description of J. Liuet al., J. Chem. Eng. Data, 2013, 58, 3557-3562.
- CTF-6 was synthesized almost in accordance with the description of Yunfeng Zhao et al., Energy Environ. Sci., 2013, 6, 3684-3692.
- the monomer and the ketjen black were mixed and then reacted in the same manner as in Example 1-1.
- the obtained CTF-3 / KB, CTF-5 / KB, and CTF-6 / KB are loaded with copper by the same method as in Example 1-2, so that the hybrid material (Cu / CTF-3 / KB, Cu / CTF-5 / KB and Cu / CTF-6 / KB).
- CTF-7 represented by the chemical formula 13 in which the triazine ring was connected by a sulfur atom was synthesized. Specifically, first, 0.235 g of trithiocyanuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 30 ml of 1,4-dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and 0.625 ml of N, N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added.
- trithiocyanuric acid manufactured by Wako Pure Chemical Industries, Ltd.
- 1,4-dioxane manufactured by Wako Pure Chemical Industries, Ltd.
- N, N-diisopropylethylamine manufactured by Tokyo Chemical Industry Co., Ltd.
- the dried powder (CTF-7 / KB) was impregnated with an aqueous solution of 5 mM K 2 [PtCl 4 ] (manufactured by Wako Pure Chemical Industries, Ltd.) at 60 ° C. for 4 hours to add platinum. Thereafter, the substrate was washed with water and acetone and then dried to obtain a hybrid material (Pt / CTF-7 / KB).
- a hybrid material (Cu / CTF-7 / KB) was obtained by supporting copper on the obtained CTF-7 / KB in the same manner as in Example 1-2.
- the molecular structure of the obtained hybrid material was analyzed by X-ray photoelectron spectrum analysis (XPS) and wide-area X-ray absorption fine structure (EXAFS) analysis. As a result, it was confirmed that CTF was formed from the bond peak, and that no peak of Pt-Pt bond was observed, so that CTF and divalent platinum 1 atom formed a coordinate bond. .
- XPS X-ray photoelectron spectrum analysis
- EXAFS wide-area X-ray absorption fine structure
- Electrochemical measurement A rotating disk electrode (RDE) containing the hybrid material synthesized in Examples 1-1 to 1-4 was prepared, and its electrochemical characteristics were evaluated.
- hybrid material powder was first dispersed in 175 ⁇ L of ethanol and 47.5 ⁇ L of Nafion® solution.
- the Nafion solution was a 5 mass% solution of a lower aliphatic alcohol mixture and water, and a product manufactured by Sigma-Aldrich was used.
- 7 ⁇ L of the solution was dropped onto a glassy carbon electrode (0.196 cm ⁇ 2 ) to prepare a working electrode.
- the hybrid material was adjusted to 0.8 mg ⁇ cm ⁇ 2 .
- Pt line and Ag / AgCl / KClsat. Were used as a counter electrode and a reference electrode, respectively. In the measurement, the rotation speed of the working electrode was 1500 rpm.
- the electrical conductivity of the hybrid material was measured using a resistivity meter (Loresta-GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
- FIGS. 2 (a) and 2 (b) The oxygen reduction potential-current curves of Pt / CTF-1 / KB synthesized in Example 1-1 are shown in FIGS. 2 (a) and 2 (b).
- FIG. 2 (b) is an enlarged view of FIG. 2 (a).
- 2 (a) and 2 (b) also show oxygen reduction potential-current curves of a material in which platinum is supported on CTF-1 without using carbon black. From the results shown in FIG. 2, it was observed that the current derived from oxygen reduction was significantly increased by supporting Pt / CTF-1 on Ketjen Black. It was confirmed from the electrical conductivity measurement that this was because the electrical conductivity was improved by being supported on ketjen black.
- FIG. 3 shows the result of comparison of oxygen reduction activity with and without ketjen black using CTF-1 containing no Pt.
- an oxygen saturated solution (pH 13) of 0.1 M NaOH was used for the measurement.
- Pt was not contained, the electrical conductivity was improved by supporting it on Ketjen Black, and the oxygen reduction current of CTF-1 was increased.
- FIG. 4 (a) shows the oxygen reduction reaction activity of the Pt / CTF-1 / KB hybrid material when methanol is present in the solution. Moreover, the result of having performed the same measurement by 20 mass% Pt / C of the comparative example 1 is shown in FIG.4 (b).
- FIG. 5 shows the result of the same measurement under the condition that the solution does not contain oxygen.
- the hybrid material containing CTF-1 does not have methanol oxidation reaction activity despite containing Pt, whereas Pt / C does not have methanol oxidation reaction. Activity was observed. This result also shows that the hybrid material containing CTF-1 has high selectivity only for the oxygen reduction reaction as described above.
- platinum clusters having a Pt—Pt bond are active in methanol oxidation.
- Pt is present as one atom coordinated to CTF-1 as shown from the above EXAFS result.
- the oxygen reduction reaction activity was similarly measured for the hybrid material of Example 1-2 (Cu / CTF-1 / KB) in which the metal of the Pt / CTF-1 / KB hybrid material was replaced with copper. The result is shown in FIG. From FIG. 6, it was found that even when copper was supported, high electrical conductivity was obtained and the oxygen reduction activity was improved.
- the electrical conductivity of the covalently bonded organic structure having a structure other than CTF-1 obtained in Examples 1-3 and 1-4 was also measured.
- Hybrid materials (Cu / CTF-3 / KB, Cu / CTF-5 / KB, and Cu / CTF-6) synthesized in Example 1-3, in which copper is supported on CTF-3, CTF-5, and CTF-6
- the measurement result of the oxygen reduction potential-current curve for / KB) is shown in FIG.
- the measurement result about Cu / CTF-7 / KB is shown in FIG. From these results, it was found that the electrical conductivity is improved even in CTF in which triazine rings are connected by phenylene or sulfur.
- the metal is held in the covalent organic structure by forming a coordinate bond between the nitrogen atom of the triazine ring of the covalent organic structure or the nitrogen atom of the pyridylene group and the metal. Therefore, for reactions in which the active site is a metal site or a site affected by metal coordination, a covalent organic structure containing a nitrogen atom of a triazine ring or a nitrogen atom of a pyridylene group is present.
- the present invention can be widely applied as in the embodiment.
- Example 2-1 a conductive hybrid material was prepared in which the elemental composition ratio of the covalently bonded organic structure and the conductor material determined by X-ray photoelectron spectroscopy was 2.39.
- the resulting mixture was then sealed in a glass tube and held at 400 ° C. for 21 hours under vacuum.
- the obtained powder was washed with 0.1 M HCl, water, THF, and acetonitrile, and then dried under reduced pressure.
- the dried powder is mixed with an aqueous solution of 1 mM K 2 [PtCl 4 ] (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at 30 ° C. for 1 hour while irradiating ultrasonic waves, so that platinum can be obtained. Added. Thereafter, the hybrid material was obtained by washing with water and acetone and then drying.
- XPS X-ray photoelectron spectroscopy
- the method for obtaining the elemental composition ratio between CTF and ketjen black, which is a conductor material will be described in more detail.
- the amount of platinum supported in the hybrid material of this example was 20.2 wt%.
- Example 2-2 a conductive hybrid material was prepared in which the elemental composition ratio of the covalently bonded organic structure and conductor material determined by X-ray photoelectron spectroscopy was 0.74. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.0258 g.
- the method for obtaining the elemental composition ratio between CTF and ketjen black, which is a conductor material will be described in more detail.
- the amount of platinum supported in the hybrid material of this example was 15.1 wt%.
- Example 2-3 a conductive hybrid material was prepared in which the elemental composition ratio between the covalently bonded organic structure and the conductor material determined by X-ray photoelectron spectroscopy was 0.30. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.129 g.
- the method for obtaining the elemental composition ratio between CTF and ketjen black, which is a conductor material will be described in more detail.
- the amount of platinum supported in the hybrid material of this example was 8.7 wt%.
- Example 2-4 a conductive hybrid material was prepared in which the elemental composition ratio of the covalently bonded organic structure and conductor material determined by X-ray photoelectron spectroscopy was 0.16. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.129 g and 2,6-dicyanopyridine was 0.0645 g.
- the method for obtaining the elemental composition ratio between CTF and ketjen black, which is a conductor material will be described in more detail.
- the amount of platinum supported in the hybrid material of this example was 5.7 wt%.
- Example 2-5 a conductive hybrid material was prepared in which the elemental composition ratio between the covalently bonded organic structure and the conductor material determined by X-ray photoelectron spectroscopy was 0.10. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.129 g and 2,6-dicyanopyridine was 0.0323 g.
- Example 2-6 a conductive hybrid material was prepared in which the elemental composition ratio of the covalently bonded organic structure and conductor material determined by X-ray photoelectron spectroscopy was 0.030. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.129 g and 2,6-dicyanopyridine was 0.0161 g.
- the method for obtaining the elemental composition ratio between CTF and ketjen black, which is a conductor material will be described in more detail.
- the amount of platinum supported in the hybrid material of this example was 2.7 wt%.
- Example 2-7 a conductive hybrid material was prepared in which the elemental composition ratio of the covalently bonded organic structure and conductor material determined by X-ray photoelectron spectroscopy was 0.0090. Specifically, a hybrid material was synthesized in the same manner as in Example 2-1, except that the amount of ketjen black added was 0.129 g and 2,6-dicyanopyridine was 0.0040 g.
- the amount of platinum supported in the hybrid material of this example was 2.4 wt%.
- FIG. 9 and 10 show the results of performing linear sweep voltammetry on the hybrid materials of Examples 2-1 to 2-7 and Comparative Example 2.
- FIG. 9 means the hydrogen oxidation catalytic activity per unit catalyst amount, and it can be said that the higher the current density, the higher the catalytic activity.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material is 0.05 to 0.50. It turns out that it is preferable.
- FIG. 10 means hydrogen generation catalytic activity per unit catalyst amount, and it can be said that the higher the current density is, the higher the catalytic activity is.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material is 0.05 to 0.50. It turns out that it is preferable. As described above, even with a catalyst having a low hydrogen generation catalytic activity, it is possible to increase the hydrogen generation catalytic activity as an electrode by appropriately increasing the amount of the catalyst supported on the electrode.
- the graph of FIG. 11 means the hydrogen oxidation catalytic activity per unit platinum amount obtained from the hydrogen oxidation catalytic activity per unit catalyst amount of FIG. 9 and the result of the composition analysis by XPS.
- the higher the HOR (Hydrogen Oxidation Reaction) current density per unit platinum amount the higher the catalytic activity per unit platinum amount.
- the HOR current density per unit platinum amount is larger than 20 wt% Pt / C. I understand.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material determined by XPS is preferably 0.005 to 1, preferably 0.005 to 0.00 from the viewpoint of current density per unit platinum amount. 60 is more preferable.
- the element composition ratio is more preferably 0.005 to 0.30, particularly preferably 0.005 to 0.10, and most preferably 0.005 to 0.05.
- the graph of FIG. 12 means the hydrogen generation catalyst activity per unit platinum amount obtained from the hydrogen generation catalyst activity per unit catalyst amount of FIG. 10 and the result of the composition analysis by XPS.
- the higher the HER (Hydrogen Evolution Reaction) current density per unit platinum amount the higher the catalytic activity per unit platinum amount.
- the HER current density per unit platinum amount is larger than 20 wt% Pt / C. I understand.
- the elemental composition ratio between the covalently bonded organic structure and the conductor material determined by XPS is preferably 0.005 to 1, preferably 0.005 to 0.00 from the viewpoint of current density per unit platinum amount. 60 is more preferable.
- the element composition ratio is more preferably 0.005 to 0.30, particularly preferably 0.005 to 0.10, and most preferably 0.005 to 0.05.
- the preferable elemental composition ratio of the covalent organic structure to the conductor material does not depend on the type of the covalent organic structure.
- Each of the covalent bond organic structures is a material having a small electrical conductivity, and the distance between the covalent bond organic structure effective for electron transfer and the conductive material is almost constant. That is, when the covalent bond organic structure is supported in the form of a film on the surface of the conductor material, the film thickness of the covalent bond organic structure effective for electron transfer is almost constant. Therefore, it is preferable that the covalently bonded organic structure is supported on the surface of the conductive material with a thin film thickness that facilitates electron transfer.
- the preferable elemental composition ratio of the covalently bonded organic structure to the conductor material of the hybrid material in the present embodiment is 0.005 to 1, and does not depend on the type of the conductor material. That is, when the specific surface area of the conductor material is smaller than that of the present embodiment, the composition ratio range works in the direction of shifting to a small value as a whole, and conversely, when the specific surface area is larger than that of the present embodiment, the composition ratio range. Is considered to work in the direction of large values.
- the preferred elemental composition ratio of the covalently bonded organic structure to the conductor material is 0.005 to 1 regardless of the type of the conductor material.
- the conductive hybrid material of the present embodiment provides excellent conductivity by supporting a covalently bonded organic structure on a conductive material such as a carbon material, and can be useful as an electrode material or the like. It is a demonstration.
- the electronic conductivity can be imparted, and the fuel cell electrode catalyst material or In addition, it can be used as a catalyst material or an electrode material with electron transfer.
- the conductive hybrid material of this embodiment can disperse
- a conductive hybrid material modified with platinum is extremely useful as a material in a fuel cell or the like using methanol.
- the covalently bonded organic structure has an advantage that it is inexpensive because it consists of only an organic substance.
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Abstract
Description
H2→2H++2e- (水素酸化反応)
2H2O+2e-→H2+2OH- (水素発生反応)
本実施形態において、「共有結合性有機構造体」は、水素、炭素、窒素、酸素、ホウ素、硫黄などの原子が共有結合のみによって連結して形成された分子である。より具体的には、共有結合性有機構造体は、同一又は異なる複数の芳香族環基が共有結合によって環状の繰返しユニットを形成した構造を有する高分子を意味する。また、共有結合性有機構造体は、当該繰返しユニットが他の1つ以上の繰返しユニットと共有結合により連続して連結された、二次元又は三次元のネットワーク構造を有する高分子も意味する。このような共有結合性有機構造体は、メゾやマイクロサイズの細孔を有する多孔質構造を有するとともに、低密度かつ優れた熱安定性を有する。
本実施形態の導電性ハイブリッド材料において、共有結合性有機構造体とともに用いられる導体材料は、当該技術分野において二次電池の電極用導電性材料として一般に用いられ得るものである。導体材料は、共有結合性有機構造体を担持することによって、当該共有結合性有機構造体に電子伝導性を付与できるものであれば特に限定されない。ただ、導体材料は炭素材料であることが好ましい。
上述のように、本実施形態の導電性ハイブリッド材料は、共有結合性有機構造体を炭素材料等の導体材料上に担持させることによって、電子伝導性を付与でき、さらに金属を原子レベルで高分散させることができる。そのため、導電性ハイブリッド材料は、当該技術分野において公知の二次電池や燃料電池における電極触媒、あるいは、その他電子移動を伴う系における触媒や電極として用いることができる。
1.導電性ハイブリッド材料の合成
化学式10に示すスキームに従って、ケッチェンブラック(KB)上に、共有結合性トリアジン構造体(CTF-1)の白金錯体を担持したハイブリッド材料を合成した。
まず、実施例1と同様に、1.363gのZnCl2、0.129gの2,6-ジシアノピリジン、及び0.129gのケッチェンブラックをグローブボックス中で混合した。
2,6-ジシアノピリジンに替えて、化学式12に示すジシアノベンゼン誘導体を用いた以外は実施例1-1と同様にして、以下の構造を有するCTF-2、CTF-4及びCTF-5をそれぞれケッチェンブラックで保持したハイブリッド材料を合成した。なお、化学式12の上段が用いたモノマーの構造を示し、下段がCTFの構造を示す。
トリアジン環を硫黄原子により連結させた、化学式13に示すCTF-7を合成した。具体的には、まず、0.235gのトリチオシアヌル酸(和光純薬工業株式会社製)を30mlの1,4-ジオキサン(和光純薬工業株式会社製)中に溶解し、0.625mlのN,N-ジイソプロピルエチルアミン(東京化成工業株式会社製)を加えた。この溶液を15℃に保持しながら、7.5mlの1,4-ジオキサン中に0.125gの2,4,6-トリクロロ-1,3,5-トリアジン(東京化成工業株式会社製)を溶解した溶液を加えた。さらにこの溶液に、0.360gのケッチェンブラック(EC600JD)を加えて、15℃で1時間、25℃で2時間、85℃で4時間還流した。得られた固体をろ過し、1,4-ジオキサン、エタノールで洗浄した後、減圧乾燥した。
市販の、20質量%の白金を炭素粉末に担持した20質量%Pt/C、及びPt-Vulcan XC-72を用いた。
1.走査型電子顕微鏡観察等
実施例1-1で調製した、白金/CTF:ケッチェンブラックの質量比が100:5、100:20、100:100となるようにしたハイブリッド材料の走査型電子顕微鏡画像を図1に示す。また、共有結合性トリアジン構造体(pure CTF)及びケッチェンブラック(pure KB)の走査型電子顕微鏡画像も図1に示す。当該SEM画像から、共有結合性トリアジン構造体とケッチェンブラックが良好に混合した導電性ハイブリッド材料が得られたことが分かる。
実施例1-1~1-4で合成したハイブリッド材料を含む回転ディスク電極(RDE)を作製し、その電気化学的特性の評価を行った。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が2.39である導電性ハイブリッド材料を調製した。
本実施例のハイブリッド材料をXPS測定することにより、ハイブリッド材料を構成する窒素と炭素の組成比(N/C)を測定した。XPS測定は、XPS装置(AXIS Ultra HAS、Kratos Analytical社製)を用いた。また、励起X線として、monochromatic Al X線(10kV)を用いた。そして、各元素についてのナロースキャン測定を行い、各ピークの面積から組成比を求めた。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.74である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.0258gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.30である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.129gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.16である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.129gとし、2,6-ジシアノピリジンを0.0645gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.10である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.129gとし、2,6-ジシアノピリジンを0.0323gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.030である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.129gとし、2,6-ジシアノピリジンを0.0161gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
本実施例では、X線光電子分光によって定量される共有結合性有機構造体と導体材料の元素組成比が0.0090である、導電性ハイブリッド材料を調製した。具体的には、ケッチェンブラックの添加量を0.129gとし、2,6-ジシアノピリジンを0.0040gとした以外は、実施例2-1と同様にしてハイブリッド材料を合成した。
20wt%の白金を炭素粉末に担持した20wt%Pt/C(HiSPEC(登録商標)-3000、Johnson Matthey Fuel Cells社製)を用いた。
まず、2.5mgのハイブリッド材料の粉末を750μLのエタノール及び50μLのNafion溶液中に加え、超音波ホモジナイザーにより分散した。Nafion溶液は、低級脂肪族アルコール混合物と水の5質量%溶液で、シグマアルドリッチ社製のものを使用した。そして、当該溶液2.1μLをグラッシーカーボン電極(0.1256cm2)に滴下し、作用電極を作製した。この際、ハイブリッド材料(触媒)のグラッシーカーボン電極上への担持量は、52.2μg/cm2であった。
Claims (19)
- 細孔を有する共有結合性有機構造体と、導体材料と、を含み、
前記共有結合性有機構造体が前記導体材料上に担持されている、導電性ハイブリッド材料。 - 前記共有結合性有機構造体は、分子内に複数のトリアジン環を有する繰返しユニットよりなる高分子である、請求項1に記載の導電性ハイブリッド材料。
- 前記共有結合性有機構造体は、アリーレン、ヘテロアリーレン又はヘテロ原子を介して、複数のトリアジン環が共有結合で連結した構造を有する、請求項1に記載の導電性ハイブリッド材料。
- 前記共有結合性有機構造体は、フェニレン又はピリジレンを介して、複数のトリアジン環が共有結合で連結した構造を有する、請求項1に記載の導電性ハイブリッド材料。
- 前記共有結合性有機構造体は、ジシアノベンゼン又はジシアノピリジンの縮合反応により得られる化合物である、請求項4に記載の導電性ハイブリッド材料。
- 前記共有結合性有機構造体は、前記導体材料上においてモノマーを重合させるin-situ反応により得られる化合物である、請求項1乃至5のいずれか一項に記載の導電性ハイブリッド材料。
- 前記導体材料は炭素材料である、請求項1乃至7のいずれか一項に記載の導電性ハイブリッド材料。
- 前記炭素材料は、グラファイト、カーボンブラック、ケッチェンブラック、アセチレンブラック、カーボンナノチューブ、グラフェン及びカーボンファイバーからなる群より選ばれる少なくとも一つである、請求項8に記載の導電性ハイブリッド材料。
- 前記炭素材料は、ナノ粒子の形態である、請求項8又は9に記載の導電性ハイブリッド材料。
- 前記共有結合性有機構造体に金属が配位する、請求項1乃至10のいずれか一項に記載の導電性ハイブリッド材料。
- 前記金属は、白金族元素又は銅である、請求項11に記載の導電性ハイブリッド材料。
- 請求項1乃至12のいずれか一項に記載の導電性ハイブリッド材料を含む電極。
- 請求項1乃至12のいずれか一項に記載の導電性ハイブリッド材料を含む触媒。
- 請求項14に記載の触媒を含み、前記共有結合性有機構造体に白金族元素が配位する、水素発生触媒。
- 前記導体材料に対する前記共有結合性有機構造体の元素組成比が、0.005~1である、請求項15に記載の水素発生触媒。
- 請求項14に記載の触媒を含み、前記共有結合性有機構造体に白金族元素が配位する、水素酸化触媒。
- 前記導体材料に対する前記共有結合性有機構造体の元素組成比が、0.005~1である、請求項17に記載の水素酸化触媒。
- 請求項14に記載の触媒を含み、前記導体材料が炭素材料である酸素還元触媒。
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