WO2022210987A1 - アンモニアの製造方法及び製造装置 - Google Patents

アンモニアの製造方法及び製造装置 Download PDF

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WO2022210987A1
WO2022210987A1 PCT/JP2022/016331 JP2022016331W WO2022210987A1 WO 2022210987 A1 WO2022210987 A1 WO 2022210987A1 JP 2022016331 W JP2022016331 W JP 2022016331W WO 2022210987 A1 WO2022210987 A1 WO 2022210987A1
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cathode
group
catalyst
electrolyte
atom
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French (fr)
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仁昭 西林
和也 荒芝
寿雄 吉田
旭 山本
章一 近藤
紀仁 志賀
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Nissan Chemical Corp
University of Tokyo NUC
Kyoto University NUC
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Nissan Chemical Corp
University of Tokyo NUC
Kyoto University NUC
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/085—Organic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to a method and apparatus for producing ammonia.
  • Non-Patent Document 1 In the method of producing ammonia from nitrogen molecules by electrolysis in a low temperature range, there is a reported example of electrolytic production of ammonia at 90 ° C. using a platinum electrode as an anode and a cathode in which ruthenium is supported on carbon felt.
  • Non-Patent Document 2 There is a reported example of producing ammonia by electrolysis using Sm 1.5 Sr 0.5 CoO 4 or the like as an ammonia generating electrode.
  • Non-Patent Documents 3 samarium (II) iodide as a reducing agent and alcohols or water as a proton source. It has been reported that ammonia was produced using a molybdenum complex supported on polystyrene resin (Non-Patent Document 4).
  • Non-Patent Document 1 operates at a low temperature range of around 90 to 100°C, so the problem was the operation at room temperature around 20 to 30°C.
  • Non-Patent Document 2 has a problem that it is not easy from the viewpoint of reuse of the electrolytic device because there is a complicated process of treating the membrane with ammonia before incorporating the Nafion membrane used as the electrolyte membrane into the electrolytic device.
  • Non-Patent Document 3 requires the use of samarium (II) iodide as the reducing agent
  • Non-Patent Document 4 requires the use of decamethylcobaltocene as the reducing agent. Since it is 3 equivalents to 1 equivalent, from the viewpoint of practical use, the problem is that recovery and recycling of these reducing agents are not easy.
  • the present invention has been made to solve the above-mentioned problems, and does not use a reducing agent, avoids the pretreatment of the electrolyte membrane, and operates at room temperature, around 20 to 30°C.
  • the main purpose is a method for manufacturing
  • the present inventors have used a complex represented by a molybdenum complex as a cathode solid catalyst, a catalyst carrier, and a reaction field forming material that constitutes a cathode catalyst layer for producing ammonia.
  • a complex represented by a molybdenum complex as a cathode solid catalyst, a catalyst carrier, and a reaction field forming material that constitutes a cathode catalyst layer for producing ammonia.
  • Non-Patent Documents 1 and 2 are examples of reports using solid catalysts. There are no reports of electrochemical production of ammonia by fabricating conjugates or gas diffusion electrodes.
  • the above-mentioned Non-Patent Document 3 reports the production of ammonia using a complex represented by a molybdenum complex or the like as a molecular catalyst. Ammonia production was reported, both of which required a reducing agent.
  • the molybdenum complex (A) has the following formula (A1), (A2) or (A3) (wherein R 1 and R 2 are each an alkyl group that may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl (optionally substituted with a group, an alkoxy group or a halogen atom).
  • the molybdenum complex (B) is represented by the following formula (B1) or (B2) (wherein R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group, an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group), which is a molybdenum complex represented by [1]. manufacturing method.
  • the molybdenum complex of (C) has the formula (C1) (wherein R 1 and R 2 are alkyl groups that may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom)
  • the method for producing ammonia according to [1] which is a molybdenum complex.
  • the molybdenum complex (D) has the formula (D1) or (D2) (Wherein, R 5 and R 6 are aryl groups that may be the same or different, R 7 is an alkyl group, and n is 2 or 3). , the method for producing ammonia according to [1].
  • the method for producing ammonia according to any one of [1] to [5], wherein the cathode solid catalyst is at least one selected from the group consisting of platinum catalyst, gold catalyst and aluminum oxide.
  • a membrane electrode assembly in which an electrolyte membrane is sandwiched and joined between a cathode catalyst layer and an anode catalyst layer,
  • the cathode catalyst layer contains a complex carried or contained in at least one selected from the group consisting of a cathode solid catalyst, a catalyst carrier, a reaction field forming material, an electron conductor, an electrolyte, and a gas diffusion layer
  • the anode catalyst layer comprises an anode solid catalyst
  • the complex is (A) 2,6-bis(dialkylphosphinomethyl)pyridine as a PNP ligand (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom on the pyridine ring is an alkyl group, an alkoxy a molybdenum complex having a group or
  • the molybdenum complex (A) has the following formula (A1), (A2) or (A3) (wherein R 1 and R 2 are each an alkyl group that may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl
  • the molybdenum complex of (B) is represented by the following formula (B1) or (B2) (wherein R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl optionally substituted with a group, an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group). electrode junction.
  • the molybdenum complex (C) has the formula (C1) (wherein R 1 and R 2 are alkyl groups that may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom) is a molybdenum complex that The membrane electrode assembly according to [7].
  • the molybdenum complex of (D) has the formula (D1) or (D2) (Wherein, R 5 and R 6 are aryl groups that may be the same or different, R 7 is an alkyl group, and n is 2 or 3). , the membrane electrode assembly according to [7].
  • the cathode solid catalyst is at least one selected from the group consisting of platinum catalyst, gold catalyst and aluminum oxide.
  • the reaction field forming material is at least one selected from the group consisting of a carbon sintered body, a nitrogen sintered body, a nitrogen carbon sintered body, a rare earth metal-carbon-based bond, and a hydrophilic polymer [7] to [11].
  • a membrane electrode assembly comprising a cathode catalyst layer, an electrolyte membrane and an anode catalyst layer according to any one of [7] to [12],
  • the cathode has a structure in which a cathode catalyst layer is bonded to one side of the electrolyte membrane and a cathode current collector is arranged outside thereof, and the anode has a structure in which an anode catalyst layer is bonded to the other side of the electrolyte membrane and has A configuration in which the anode current collector is arranged on the outside, the cathode comprises a cathode catalyst layer and a cathode current collector; the anode comprises an anode catalyst layer and an anode current collector; A cathode electrolyte bath in liquid contact with the cathode, An anode electrolyte bath in liquid contact with the anode, A power supply that supplies electrons to the cathode, An ion source that supplies ions to the
  • a membrane electrode assembly comprising a cathode catalyst layer, an electrolyte membrane and an anode catalyst layer according to any one of [7] to [12],
  • the cathode has a structure in which a cathode catalyst layer is bonded to one side of the electrolyte membrane and a cathode current collector is arranged outside thereof, and the anode has a structure in which an anode catalyst layer is bonded to the other side of the electrolyte membrane and has A configuration in which the anode current collector is arranged on the outside, the cathode comprises a cathode catalyst layer and a cathode current collector; the anode comprises an anode catalyst layer and an anode current collector; An anode electrolyte bath for an anode electrolyte in liquid contact with the anode of the membrane electrode assembly, A power supply that supplies electrons to the cathode, An ion source that supplies ions to the cathode, comprising means for supplying nitrogen gas to the
  • the complex is (A) 2,6-bis(dialkylphosphinomethyl)pyridine as a PNP ligand (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom on the pyridine ring is an alkyl group, an alkoxy a molybdenum complex having a group or a halogen atom), (B) N,N-bis(dialkylphosphinomethyl)dihydrobenzimidazolidene as a PCP ligand (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom on the benzene ring is an alkyl molybdenum complex having a group, an alkoxy group or a halogen
  • the molybdenum complex (A) has the following formula (A1), (A2) or (A3) (wherein R 1 and R 2 are each an alkyl group that may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl
  • the gas diffusion electrode according to [15] which is a molybdenum complex represented by a group, an alkoxy group, or a halogen atom).
  • the molybdenum complex (B) is represented by the following formula (B1) or (B2) (wherein R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group, an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group), the gas according to [15], which is a molybdenum complex represented by diffusion electrode.
  • the molybdenum complex of (C) has the formula (C1) (wherein R 1 and R 2 are alkyl groups that may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom)
  • the gas diffusion electrode according to [15] which is a molybdenum complex.
  • the molybdenum complex (D) has the formula (D1) or (D2) (Wherein, R 5 and R 6 are aryl groups that may be the same or different, R 7 is an alkyl group, and n is 2 or 3). , the gas diffusion electrode according to [15].
  • the cathode solid catalyst is at least one selected from the group consisting of platinum catalyst, gold catalyst and aluminum oxide.
  • the reaction field forming material is at least one selected from the group consisting of a carbon sintered body, a nitrogen sintered body, a nitrogen carbon sintered body, a rare earth metal-carbon-based bond and a hydrophilic polymer, [15] to [19]. ]
  • the gas diffusion electrode according to any one of the above.
  • a gas diffusion electrode which is the cathode catalyst layer according to any one of [15] to [20]
  • a cathode current collector is disposed on one side of the cathode catalyst layer, which is the gas diffusion electrode, and an electrolyte bath is provided in liquid contact with the cathode catalyst layer,
  • the cathode comprises a cathode catalyst layer and a cathode current collector;
  • the anode is a metal plate electrode,
  • a power supply that supplies electrons to the cathode,
  • An ion source that supplies ions to the cathode, A means for supplying nitrogen gas to the electrolyte or the cathode,
  • the ion source is an electrolytic solution, and an ammonia production apparatus in which ammonia is produced from nitrogen molecules by electrolysis.
  • a cathode membrane electrode assembly in which a cathode catalyst layer is joined to one side of an electrolyte membrane,
  • the cathode catalyst layer contains a complex carried or contained in at least one selected from the group consisting of a cathode solid catalyst, a catalyst carrier, a reaction field forming material, an electron conductor, an electrolyte, and a gas diffusion layer,
  • the complex is (A) 2,6-bis(dialkylphosphinomethyl)pyridine as a PNP ligand (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom on the pyridine ring is an alkyl group, an alkoxy a molybdenum complex having a group or a halogen atom), (B) N,N-bis(dialkylphosphinomethyl)dihydrobenzimidazolidene as a PCP ligand (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom
  • the molybdenum complex (A) has the following formula (A1), (A2) or (A3) (wherein R 1 and R 2 are each an alkyl group that may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl (optionally substituted with a group, an alkoxy group or a halogen atom).
  • the molybdenum complex (B) is represented by the following formula (B1) or (B2) (wherein R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl optionally substituted with a group, an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group).
  • Membrane electrode assembly wherein R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl optionally substituted with a group, an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoro
  • the molybdenum complex of (C) has the formula (C1) (wherein R 1 and R 2 are alkyl groups which may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom)
  • the cathode membrane electrode assembly according to [22] which is a molybdenum complex.
  • the molybdenum complex (D) has the formula (D1) or (D2) (Wherein, R 5 and R 6 are aryl groups that may be the same or different, R 7 is an alkyl group, and n is 2 or 3). , the cathode membrane electrode assembly according to [22].
  • the cathode solid catalyst is at least one selected from the group consisting of platinum catalyst, gold catalyst and aluminum oxide.
  • the reaction field forming material is at least one selected from the group consisting of a sintered carbon body, a sintered nitrogen body, a sintered nitrogen carbon body, a rare earth metal-carbon-based bond, and a hydrophilic polymer [22] to [26].
  • the cathode membrane electrode assembly according to any one of [28] A cathode membrane electrode assembly having a cathode catalyst layer bonded to one side of the electrolyte membrane according to any one of [22] to [27]; a cathode current collector is disposed on the opposite side of the cathode catalyst layer to the electrolyte membrane; the cathode comprises a cathode catalyst layer and a cathode current collector; Equipped with an electrolyte bath that is in liquid contact with the electrolyte membrane, the anode is a metal plate electrode, A power supply that supplies electrons to the cathode, An ion source that supplies ions to the cathode, A means for supplying nitrogen gas to the electrolyte or the cathode, the ion source is an electrolyte membrane, an electrolyte, or both an electrolyte membrane and an electrolyte; Ammonia production equipment that produces ammonia from nitrogen molecules by electrolysis.
  • the cathode solid catalyst, the catalyst carrier, the reaction field forming material, the electron conductor In the presence of a complex supported on at least one selected from the group consisting of an electrolyte and a gas diffusion layer, a supply of electrons from a power source, a supply of ions from an ion source, and nitrogen molecules from means for supplying nitrogen gas.
  • Ammonia can be produced by supplying
  • FIG. 1 is an explanatory diagram of an ammonia electrolyzer (No. 1);
  • FIG. FIG. 2 is an explanatory diagram of an ammonia electrolyzer (No. 2); It is explanatory drawing of the electrolytic device (3) of ammonia. It is explanatory drawing of the electrolytic device (4) of ammonia. It is a chart of IR measurement of the sintered body (a1). It is a chart of IR measurement of Ketjenblack EC (EC300J). It is explanatory drawing of the electrolytic device (5) of ammonia.
  • FIG. 10 is a general view of a carbon separator used in the electrolytic device (No. 5).
  • FIG. 11 is a general view of a gasket used in the electrolytic device (No. 5).
  • n- is normal, “s-” is secondary, “t-” is tertiary, “o-” is ortho, “m-” is meta, and “p-” is Para, “Me” for a methyl group, “t-Bu” for a t-butyl group, “Ph” for a phenyl group, “S” for a sulfur atom, “O” for an oxygen atom, “Si” represents a silicon atom.
  • supporting a catalyst as used in the specification includes not only cases where a solid catalyst is adhered to a carrier, but also cases where a liquid or gaseous catalyst is contained in a medium.
  • C a -C b alkyl group is a monovalent alkyl group produced by losing one hydrogen atom from a linear, branched or cyclic aliphatic hydrocarbon having a to b carbon atoms.
  • n-octyl group represents a group such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-ethylpentyl group, n-octyl group, 2,2,4-trimethylpentyl group, 2,5-dimethylhex
  • a C a -C b alkoxy group represents a monovalent group in which the above-described alkyl group having a to b carbon atoms is bonded to oxygen, for example, a methoxy group , ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, cyclobutoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, t-pentoxy group, 1,1-dimethylpropoxy group, cyclopentoxy group, n-hexythoxy group, isohexyxy group, 3-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, cyclohexy Specific examples include thoxy group, n-heptoxy group, 2-methylhexyoxy group, 3-ethylp
  • halogen atoms in the present specification include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.
  • Ar 6 aryl group in this specification represents a monovalent group formed by losing one hydrogen atom from an aromatic ring of an aromatic hydrocarbon having 6 carbon atoms, such as a phenyl group, from the 2-position
  • examples thereof include a phenyl group having a substituent at least one of the 6-positions.
  • Substituents on the aromatic ring of Ar 6 aryl include halogen atoms such as fluoro, chloro, bromo and iodo groups, methyl group, trifluoromethyl group, ethyl group, n-propyl group and isopropyl group, Examples include n-butyl group, isobutyl group, s-butyl group and t-butyl group.
  • Ar 6 aryl group examples include a phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluorophenyl group, fluoromethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p- tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-(t-butyl)phenyl group, m-(t-butyl)phenyl group, m
  • the method for producing ammonia according to the present embodiment can be carried out in a production apparatus that performs electrolysis.
  • a production apparatus that performs electrolysis is sometimes referred to as an electrolytic apparatus, and is composed of an electrolytic cell, a nitrogen gas supply means, an ammonia recovery means, and an exhaust gas removal means. Details of the electrolytic apparatus will be described later.
  • the electrolytic cell is composed of an electrode, an electrolyte bath, a nitrogen gas supply port, and an exhaust gas outlet.
  • the anode is the electrode in which the oxidation reaction occurs
  • the cathode is the electrode in which the reduction reaction occurs.
  • the complex is at least one selected from the group consisting of a cathode solid catalyst, a catalyst carrier, a reaction field forming material, an electron conductor, an electrolyte, and a gas diffusion layer.
  • a cathode solid catalyst a catalyst carrier
  • a reaction field forming material an electron conductor
  • an electrolyte a gas diffusion layer.
  • a cathode solid catalyst supported on a catalyst carrier, supported on a reaction field forming material, supported on an electron conductor, and supported on a gas diffusion layer.
  • supported on a cathode solid catalyst and a catalyst carrier supported on a cathode solid catalyst and a reaction field forming material; supported on a cathode solid catalyst and an electron conductor; on a cathode solid catalyst and a gas diffusion layer supported form, supported on catalyst carrier and reaction field forming material, supported on catalyst support and electron conductor, supported on catalyst support and gas diffusion layer, reaction field forming material and electron conductor a form supported on a reaction field forming material and a gas diffusion layer; a form supported on an electron conductor and a gas diffusion layer; a form supported on an electron conductor and a gas diffusion layer; a form supported on an electron conductor and a gas diffusion layer; a form supported on a cathode solid catalyst, a catalyst carrier and a reaction field forming material; Form supported on cathode solid catalyst, reaction
  • Supporting methods in the catalyst body include support by physical adsorption, support by electrostatic interaction, support by chemical bonding, support by encapsulation, support by metal organic coordination polymer, and metal organic frameworks (Metal Organic Frameworks, MOF and may be abbreviated), and between the complex and the material constituting the cathode catalyst layer, one type of supporting method may be used, or two types of supporting methods may be used.
  • the carrying method described above may be used.
  • the material constituting the cathode catalyst layer in this specification means the cathode solid catalyst, the reaction field forming material, the catalyst carrier, the electron conductor, the electrolyte, and the gas diffusion layer.
  • At least one of them is preferably supported by chemical bonding, supported by encapsulation, supported by a metal-organic coordination polymer, or supported by MOF, and is more preferably supported by chemical bonding.
  • Chemical bonds include covalent bonds, ionic bonds, coordinate bonds, metallic bonds, and the like, depending on the bonding mechanism.
  • the complex is composed of a ligand and molybdenum, which is a central metal.
  • molybdenum which is a substituent on the ligand or the central metal of the complex, constitutes a cathode catalyst layer.
  • the surface functional groups in the material are physically adsorbed or electrostatically interacted, but the support by physical adsorption or electrostatic interaction is preferable from the viewpoint of durability and performance in the electrolytic device that produces ammonia.
  • the complex gradually flows out into the electrolytic solution, etc. during the reaction, and a problem that the complex moves to a place where it cannot receive ions such as protons and electrons in the catalyst layer as the reaction time progresses.
  • the problem is that the complex flows out and moves. is suppressed.
  • the part responsible for ammonia synthesis and the part serving as the skeleton for supporting the catalyst may be the same or different. This is a method with a degree of freedom in design.
  • the method of supporting a complex represented by the above molybdenum complex on a cathode solid catalyst, a reaction field forming material, a catalyst carrier, an electron conductor, or a gas diffusion layer is carried out by chemical bonding of the above complex with a ligand. is preferred.
  • a method for supporting a complex represented by the molybdenum complex or the like on an electrolyte it is preferable to support the complex by chemical bonding with a ligand.
  • an ionic liquid is used as the electrolyte
  • the relationship due to electrostatic interaction between the anion site of the ionic liquid and the cation site of the metal of the complex is defined as support in a broad sense.
  • these are based on conventional techniques, and there is a problem of outflow and migration of the complex.
  • the complex in the method for producing ammonia of the present embodiment includes (A) 2,6-bis(dialkylphosphinomethyl)pyridine as a PNP ligand (wherein the two alkyl groups may be the same or different, and the pyridine ring at least one hydrogen atom on which may be substituted with an alkyl group, an alkoxy group or a halogen atom), (B) N,N-bis(dialkylphosphinomethyl)dihydrobenzo as a PCP ligand Molybdenum complex having imidazolidene (provided that the two alkyl groups may be the same or different, and at least one hydrogen atom on the benzene ring may be substituted with an alkyl group, an alkoxy group, or a halogen atom), ( C) molybdenum complexes with bis(dialkylphosphinoethyl)arylphosphines as PPP ligands, where the two alkyl groups can be the same or
  • the molybdenum complex (A) will be described.
  • the alkyl group of the molybdenum complex (A) include C 1 to C 10 alkyl groups, preferably having 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and an isopropyl group. , t-butyl group and cyclohexyl group are even more preferred.
  • the alkoxy group includes, for example, a C 1 to C 8 alkoxy group and a benzyloxy group, preferably having 1 to 8 carbon atoms, and when the alkoxy group is a benzyloxy group.
  • the benzyloxy group may have at least one hydrogen atom on the benzene ring substituted with a resin.
  • Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • R 1 and R 2 are each an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl optionally substituted with a group, an alkoxy group or a halogen atom).
  • alkyl group, the alkoxy group and the halogen atom include those already exemplified.
  • R 1 and R 2 are preferably bulky alkyl groups such as t-butyl, isopropyl or cyclohexyl.
  • the hydrogen atoms on the pyridine ring are preferably unsubstituted or substituted with a C 1 -C 10 alkyl group, a C 1 -C 8 alkoxy group or a benzyloxy group at the 4-position hydrogen atom.
  • More preferred alkoxy groups include benzyloxy groups in which at least one hydrogen atom on the benzene ring is substituted with a resin, and the resins include chloromethyl resins (eg, polymer-bound 5-[4-(chloro methyl)phenyl]pentyl]styrene, polymer-bound 4-(benzyloxy)benzyl chloride, polymer-bound 4-methoxybenzhydryl chloride), (chloromethyl)polystyrene, Merrifield resin, JandaJel-Cl (registered trademark), etc. is mentioned. Of these, (chloromethyl) polystyrene, Merrifield resin and JandaJel-Cl® are preferred.
  • chloromethyl resins eg, polymer-bound 5-[4-(chloro methyl)phenyl]pentyl]styrene, polymer-bound 4-(benzyloxy)benzyl chloride, polymer-bound 4-methoxybenzhydryl chloride
  • the molybdenum complex (B) will be described.
  • the molybdenum complex (B) has the following formula (B1) or (B2) (wherein R 1 and R 2 are each a C 1 -C 10 alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and the molybdenum complex of (B1) at least one hydrogen atom on the benzene ring of may be substituted with a C 1 -C 10 alkyl group, a C 1 -C 8 alkoxy group or a halogen atom).
  • Examples of the C 1 -C 10 alkyl group, the C 1 -C 8 alkoxy group and the halogen atom include those already exemplified.
  • R 1 and R 2 are preferably bulky alkyl groups such as t-butyl, isopropyl or cyclohexyl.
  • R 3 and R 4 in the molybdenum complex of (B2) each independently represent an electron withdrawing group, and R 3 and R 4 may be electron withdrawing groups, and when R 3 is an electron withdrawing group , R 4 may be a hydrogen atom.
  • An electron-withdrawing group is also called an electron-withdrawing group or an electron-accepting group. It is a theory that focuses on changes in the electron density and bonding state of a substance and tries to interpret it as unified as possible. By effect, it refers to a substituent that attracts electrons from the bonding electron side compared to a hydrogen atom.
  • Examples of the electron-withdrawing group include substituents that have an electron-donating mesomeric effect but that greatly contribute to the electron-withdrawing inductive effect, and substituents that have electron-withdrawing mesomeric and inductive effects.
  • substituents that contribute significantly to the electron-withdrawing properties of the inductive effect include fluorine, chlorine, bromine, iodine, —CH 2 Cl, or —CH ⁇ CHNO 2 .
  • substituents having electron-withdrawing mesomeric and inductive effects include quaternary ammonium groups, trifluoromethyl groups, perfluoroalkyl groups, trichloromethyl groups, and cyano groups with anions as counterions.
  • quaternary ammonium group examples include trialkylammonium groups, such as trimethylammonium group, triethylammonium group, tributyl An ammonium group etc. are mentioned.
  • Counter ions for the nitrogen atoms constituting the quaternary ammonium group include hexafluorophosphate ion, hexachloroantimonate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, phosphate ion, sulfonate ion, chloride, bromide, iodide, hydroxide and the like.
  • R 3 and R 4 are preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a trifluoromethyl group, more preferably a chlorine atom and a trifluoromethyl group.
  • the molybdenum complex (C) will be described.
  • the molybdenum complex of (C) for example, the formula (C1) (wherein R 1 and R 2 are C 1 -C 10 alkyl groups which may be the same or different, R 5 is an Ar 6 aryl group, X is an iodine atom, a bromine atom or a chlorine is an atom).
  • R 1 and R 2 are preferably bulky alkyl groups such as t-butyl, isopropyl or cyclohexyl.
  • a phenyl group is preferred as R5 .
  • the molybdenum complex (D) will be described.
  • the formula (D1) or (D2) (wherein R 5 and R 6 are Ar 6 aryl groups, which may be the same or different, R 7 is a C 1 -C 10 alkyl group, and n is 2 or 3); Molybdenum complexes represented by The Ar 6 aryl group and the C 1 -C 10 alkyl group are the same as those already exemplified.
  • R 5 and R 6 are phenyl groups and R 7 is a C 1 -C 4 alkyl group.
  • R 5 and R 6 are phenyl groups and n is 2.
  • the catalyst body in which the complex is supported on the material constituting the cathode catalyst layer is represented by, for example, formulas (Z1) to (Z4) (In the formulas (Z1) to (Z4), Z is the surface of the material constituting the cathode catalyst layer, and depending on the type of the material, the surface may be a hydrogen atom, a metal atom, or a hydroxyl group.
  • MC is a divalent group formally replacing one hydrogen atom in the structure of the ligand of the complex selected from the group consisting of molybdenum complexes (A), (B), (C) and (D) above.
  • L is a divalent group, oxygen atom (-O-), sulfur atom (-S-), "-(CH 2 ) m - (m represents an integer of 1 to 20)", “- (OCH 2 CH 2 ) n — (n represents an integer of 1 to 150.)”, formulas (L1) to formulas (L18), or divalent groups such as formula (L19), or these divalent represents a divalent group in which two or more groups are bonded, R Si and R N are each independently a C 1 -C 4 alkyl group; T is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an amino group, a propargyl group, or selected from the group consisting of the ionic liquids described in formulas (IL1) to (IL7) above;
  • c, c1, and c2 are each independently an integer of 1 or more, t is an integer of 0 or more. ) and the catalyst body represented by.
  • the catalyst in the ammonia production method of the present embodiment is not particularly limited, but when the complex is supported on a metal catalyst or a metal electrode, for example, formulas (Ms1) to (Ms3) (In the formulas (Ms1) to (Ms3), M is a metal atom, such as platinum, gold, silver, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, metals such as manganese, vanadium, molybdenum, gallium, aluminum, and alloys thereof; m1 and m2 are each independently an integer of 1 or more, m, c, t, MC and T are the same as above. ) and the catalyst body represented by Examples of the metal catalyst include metal particles, metal nanoparticles, and the like, with metal nanoparticles being preferred.
  • step 1 referring to Non-Patent Document Synthesis, 2017, vol. 49, pp. 1327-1334, Buchwald's catalyst system using palladium (II) acetate and the phosphorus ligand described in formula (SPhos) was used.
  • a compound represented by the formula ( ⁇ 3) can be obtained by a Suzuki coupling reaction followed by a hydrolysis reaction of the ester group.
  • the compound represented by the formula ( ⁇ 1 ) can be obtained by the method described in Non-Patent Document Chem. Lett. 2019, Vol. , a C 1 to C 4 alkyl group) are available from reagent manufacturers, for example, ethyl 4-bromobenzoate is available from Tokyo Kasei Kogyo Co., Ltd.
  • step 2 referring to Non-Patent Document Tetrahedron, 1999, Vol. -4-Methylmorpholinium chloride n-hydrate (compound represented by formula (DMT-MM))” triazine condensing agent (for example, available from Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd.).
  • AuNP1 gold nanoparticles having an amino group represented by the formula ( AuNP1 ) are available from Sigma-Aldrich Japan LLC. (Catalog number 765260)" can be used. In the case of PEG 3000, n is approximately 50-80. In step 3, referring to Non-Patent Document Chem. Ms4) can be synthesized.
  • Gold nanoparticles having an amino group represented by the formula (AuNP1) can be mentioned, and can be obtained and used from NanoHybrids (https://nanohybrids.net/pages/corporate). Average particles can be selected from 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 60 nm, 80 nm, using 5 kDa polyethylene glycol, and n is on the order of 100-130.
  • gold nanoparticles having amino groups can be synthesized by referring to the method described in the non-patent literature International Journal of Nanomedicine, 2016, Vol. 11, pp. 791-822. The value of n and the value of c can be adjusted as appropriate.
  • step 1 a compound represented by the formula ( ⁇ 3) can be obtained by performing a Williamson ether synthesis reaction using a potassium carbonate base. Williamson ether synthesis can be carried out with reference to the description of the review in Chem. Rev. 1934, Vol.
  • the compound represented by the formula ( ⁇ 1) can be obtained by the method described in Non-Patent Document Chem. Lett. 2019, Vol. -1-propyne is available from Fujifilm Wako Pure Chemical Industries.
  • gold nanoparticles having an azide group represented by the formula (AuNP4) can be obtained with reference to Non-Patent Document Org.Biomol.Chem., 2021, Vol.
  • gold nanoparticles represented by the formula (AuNP3) can be obtained from Sigma-Aldrich Japan G.K. ” can be used.
  • the compound represented by formula ( ⁇ 4) can be obtained by the method described in Chem.Commun., 2015, Vol. In step 3, referring to Non-Patent Document Bioconjugate Chem., 2010, Vol. 21, pp. 1912-1916, azide-alkyne is prepared at a low catalytic amount in which a water-soluble ligand stabilizes copper (I) ions.
  • Gold nanoparticles represented by the formula (AuNP5) can be obtained by performing a Huisgen 1,3-dipolar cycloaddition reaction.
  • the water-soluble ligand, tris(3-hydroxypropyltriazolylmethyl)amine, is available from Tokyo Chemical Industry Co., Ltd.
  • step 4 referring to Non-Patent Document Chem. Ms5) can be synthesized.
  • the catalyst in the ammonia production method of the present embodiment is not particularly limited, but in the case where the complex is supported on a metal oxide, for example, formulas (MO1) to (MO9)
  • M is a metal atom, such as aluminum, zirconium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, cerium, Metals such as samarium, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, gold, magnesium, and silicon, and metals in which these are combined.
  • Metal oxides include M x O y (metal oxide x and y are each independently set as integers according to Dalton's law through various manufacturing reactions of products.) When combining metal oxides, for example, a double oxide composed of silicon and aluminum silica-alumina, silica-magnesia which is a double oxide composed of silicon and magnesium, etc. m, c1, c2 and MC are the same as above. ) and the catalyst body represented by.
  • step 1 using the triazine-based condensing agent represented by the formula (DMT-MM), amino groups on the surface of the nanoparticles represented by the formula (FeSiNP1) and 4 represented by the formula ( ⁇ 4) -By carrying out an amide formation reaction with the carboxyl group of bromobenzoic acid, nanoparticles represented by the formula (FeSiNP2) can be obtained.
  • DMT-MM triazine-based condensing agent represented by the formula (DMT-MM)
  • amino groups on the surface of the nanoparticles represented by the formula (FeSiNP1) and 4 represented by the formula ( ⁇ 4) -By carrying out an amide formation reaction with the carboxyl group of bromobenzoic acid, nanoparticles represented by the formula (FeSiNP2) can be obtained.
  • the nanoparticles represented by the formula (FeSiNP1) are silica-coated iron oxide magnetic nanoparticles that can be obtained by the method described in Non-Patent Document Org. Lett.
  • the iron oxide magnetic nanoparticles are composed of at least one of maghemite and magnetite with a diameter of 1-100 nm, and the magnetic nanoparticles with a size of 2-20 nm exhibit superparamagnetism in the absence of a magnetic field and can be magnetized by an external magnetic source. It is known to be produced, and can be used for purification when producing the catalyst body in the method for producing ammonia of the present embodiment.
  • iron oxide magnetic nanoparticles are available, for example, from Sigma-Aldrich Japan LLC and are described as "Iron oxide (II, III) magnetic nanoparticles solution 5 nm avg. part. size (TEM), carboxylic acid functionalized, 5 mg/mL Fe in H 2 O, dispersion”, “Iron (II, III) oxide, magnetic nanoparticles solution 10 nm avg. part. size (TEM), carboxylic acid functionalized, 5 mg/mL Fe in H 2 O, dispersion”, “ Iron (II, III) oxide, magnetic nanoparticle solution 10 nm avg. part.
  • TEM TEM
  • amine functionalized 1 mg/mL Fe in H 2 O, dispersion
  • Iron (II, III) oxide magnetic nanoparticle particle solution 5 nm avg. part. size (TEM)
  • PEG functionalized 1 mg/mL Fe in H 2 O, dispersion
  • 4-bromobenzoic acid represented by formula ( ⁇ 4) is available from Tokyo Chemical Industry Co., Ltd. available from the company.
  • the nanoparticles represented by the formula (FeSiNP3) can be obtained by performing the Suzuki coupling reaction using the Buchwald catalyst system.
  • the phosphorus ligand described in formula (SPhos) is the same as described above.
  • step 3 the deselenization reaction and the complex formation reaction of the molybdenum metal with the PNP ligand are performed to synthesize the catalyst body of the formula (MO10).
  • steps 1 to 3 when washing and purifying the nanoparticles obtained after the reaction, it is possible to use a magnet to collect the obtained nanoparticles in an external magnetic field for washing. It can be easily implemented.
  • step 1 a compound represented by formula (d2) can be obtained by performing a Williamson ether synthesis reaction using sodium hydride.
  • the compound represented by formula (d1) can be obtained by the method described in Non-Patent Document Chem. Lett.
  • step 2 the compound represented by the formula (d3) can be obtained by deprotecting the trityl group, which is the protective group for the thiol group.
  • step 3 a deselenization reaction can be performed to obtain a compound represented by the formula (d4) with reference to Non-Patent Document Chem. Lett. 2019, Vol. In step 4, referring to Non-Patent Document RSC Adv. 2018, Vol. 8, pp. 24021-24028, aluminum oxide represented by formula (SC0) is used, and tetrachloroauric (III) acid is used as a raw material.
  • an alumina-supported gold catalyst represented by formula (SC1) can be prepared.
  • step 5 the thiol group of the compound represented by formula (d4) is reacted with the gold atom on the surface of the alumina-supported gold catalyst represented by formula (SC1) to obtain the compound represented by formula (5). can be obtained to obtain PNP ligand derivatives.
  • step 6 with reference to Non-Patent Document Chem. Catalytic bodies can be synthesized.
  • [M] in the formula of the reaction pathway represents a complex that can generate ammonia. It has been reported that a complex having a catalytic cycle of is excellent in catalytic activity for ammonia production.
  • the structure of the catalyst body represented by the following is preferable and important, that is, a catalyst body capable of promoting the formation of a molybdenum dinuclear complex in which nitrogen molecules are crosslinked with the molybdenum complex.
  • the structure of the catalyst body represented by the formula (d6-A1-N 2 ) is not limited as long as the production of ammonia proceeds.
  • the new reaction pathway can reduce three protonation reactions and three reduction reactions, so from the viewpoint of accelerating the ammonia production reaction , via the structure of the catalyst body represented by the formula (d6-A1-N 2 ) and via the scission reaction of the bridged nitrogen molecule is preferred.
  • a specific example of the method for synthesizing the catalyst in the method for producing ammonia of the present embodiment will be described with reference to the diagram below, taking the catalyst represented by the formula (dA2) as an example.
  • the catalyst represented by the formula (dA2) is a catalyst obtained by reacting a thiol compound represented by the formula (T1) with the catalyst represented by the formula (dA1).
  • c is the same as above, and c' is an integer of 1 or more.
  • the thiol group of the thiol compound represented by the formula (T1) reacts with the gold atom on the surface of the alumina-supported gold catalyst to generate a gold thiol bond, and the dimethoxy(methyl)silyl groups generate a siloxane bond.
  • the catalyst represented by the formula (dA2) can be obtained.
  • an example of the structure obtained by reacting the catalyst represented by the formula (d6-A1-N 2 ) with the thiol compound represented by the formula (T1) is represented by the formula (d7- A1-N 2 ) is shown as a catalyst body.
  • the catalyst ink containing the thiol compound and the formula (dA1) or the formula (d6-A1-N 2 ) is coated on the gas diffusion electrode, and then placed on the electrolyte membrane and thermocompression bonded to obtain the formula (dA2) or formula (d7-A1-N 2 ).
  • the represented catalyst bodies can be fabricated in the cathode catalyst layer. It is believed that the acid component and moisture necessary for forming the siloxane bond by the dimethoxy(methyl)silyl group are supplied from the acid group and moisture contained in the electrolyte membrane. In order to sufficiently promote the siloxane bonding, dilute sulfuric acid may be used to condition the catalyst layer after the electrolysis apparatus is assembled.
  • solvents used in preparing the catalyst ink include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, dimethylsulfoxide, Examples include compounds selected from N,N-dimethylformamide, chloroform, dichloromethane, diethyl ether, 1,4-dioxane, tetrahydrofuran, and ionic liquids described later.
  • thiol compound for producing the catalyst body of the present embodiment 3-(diethoxymethylsilyl)-1-propanethiol and 3-(dimethoxymethylsilyl) are used in addition to the thiol compound represented by the formula (T1).
  • Compounds such as 2-methyl-1-propanethiol, 3,3′-(dimethoxymethylsilyl)bis-1-propanethiol can be used.
  • the cathode catalyst layer 103 (shown in FIGS. 1 to 4 and 7) for producing ammonia of the present embodiment includes a complex, a cathode solid catalyst, a catalyst carrier, a reaction field forming material, an electron conductor, an electrolyte, and a gas diffusion layer.
  • the cathode catalyst layer 103 is sometimes referred to as a gas diffusion electrode 133 in this specification.
  • the solid catalyst in the method for producing ammonia of the present embodiment is a metal catalyst having a single composition or a mixture of a plurality of metal components such as an alloy catalyst, and a metal oxide of a typical element.
  • metal catalysts and oxides it may be used as a solid catalyst in combination with a catalyst.
  • the solid catalyst may be used as an electron conductor, and the oxide catalyst may be used as a support for the metal catalyst.
  • Examples of solid catalysts in the method for producing ammonia of the present embodiment include metal catalysts such as platinum catalysts, gold catalysts, silver catalysts, ruthenium catalysts, iridium catalysts, rhodium catalysts, palladium catalysts, osmium catalysts, tungsten catalysts, and lead catalysts. , iron catalysts, chromium catalysts, cobalt catalysts, nickel catalysts, manganese catalysts, vanadium catalysts, molybdenum catalysts, gallium catalysts, aluminum catalysts, and alloys thereof.
  • Examples of oxide catalysts include aluminum oxide and zirconium oxide.
  • the solid catalyst used on the cathode side is defined as a cathode solid catalyst
  • preferable cathode solid catalysts are platinum catalyst, gold catalyst, iridium catalyst, palladium catalyst, molybdenum catalyst, zinc oxide, aluminum oxide, molybdenum oxide, and cerium oxide.
  • platinum catalyst gold catalyst, iridium catalyst, palladium catalyst, molybdenum catalyst, zinc oxide, aluminum oxide, molybdenum oxide, and cerium oxide.
  • samarium oxide more preferably platinum catalyst, gold catalyst, zinc oxide, aluminum oxide, cerium oxide and samarium oxide, still more preferably platinum catalyst, gold catalyst, aluminum oxide, molybdenum oxide, and samarium oxide.
  • the combination of the complex and the cathode solid catalyst in the catalyst body used in the cathode catalyst layer 103 for producing ammonia of the present embodiment can be arbitrarily combined from the complex and the cathode solid catalyst.
  • preferred combinations are "platinum catalyst, linker, molybdenum complex of formula (A1)", “gold catalyst, linker, molybdenum complex of formula (A1)", “[gold catalyst and platinum catalyst], linker, formula ( Molybdenum complex of A1)”, “[gold catalyst and aluminum oxide], linker, molybdenum complex of formula (A1)", “[gold catalyst, platinum catalyst and aluminum oxide], linker, molybdenum complex of formula (A1)", “platinum catalyst, linker, molybdenum complex of formula (B2)", “gold catalyst, linker, molybdenum complex of formula (B2)", “[gold catalyst and platinum catalyst], linker, molybdenum complex of formula (B2)", Combinations with "[gold catalyst and aluminum oxide], linker, molybdenum
  • the catalyst carrier in the cathode catalyst layer 103 of this embodiment may be responsible for at least one of electronic conduction and ion conduction, and is not particularly limited as long as it supports the catalyst of this embodiment.
  • Ion-conducting substances include at least one of protons and hydroxonium ions, or hydroxide ions.
  • catalyst carriers include carbon black, carbon nanotubes, carbon materials, metal meshes, metal foams, metal oxides, multiple oxides, polymer electrolytes, and ionic liquids. may be used in combination. Further, when the catalyst carrier is used in the electrode, it not only plays the role of supporting the catalyst, but also participates as a catalyst or co-catalyst in the reaction occurring at the electrode.
  • the catalyst carrier has a large specific surface area because it may play a role in increasing the effective surface area of the catalyst, increasing the number of active points, and optimizing the arrangement state of the active points by dispersing the catalyst components. From the viewpoint of using a solid or porous material, it may be used by selecting from the following.
  • Examples of carbon black as a catalyst carrier in the cathode catalyst layer 103 of the present embodiment include Ketjen black, Ketjen black EC, channel black, oil furnace black, vulcan, furnace black, thermal black, acetylene black, and lamp black. , graphitized black, oxide black, etc., and acetylene black, Ketjenblack, and Ketjenblack EC are preferred, and Ketjenblack and Ketjenblack EC are more preferred because of their good conductivity.
  • One type of carbon black may be used alone, or two or more types may be used in combination. Carbon black may be surface-treated.
  • carbon nanotubes for example, vapor growth, catalytic vapor growth, catalytic chemical vapor deposition, chemical vapor deposition, super multiplication, catalytic carbon deposition, arc discharge, laser evaporation, etc.
  • the resulting single-walled nanotubes and multi-walled carbon nanotubes can be exemplified, and these can take any form such as a needle-like, coil-like, or tube-like form.
  • the carbon nanotube tube it has a cylindrical shape by winding one sheet of graphite with a carbon hexagonal network surface, and it is a multi-wall carbon nanotube wound in three or more layers (multi-wall carbon nanotube), one of graphite.
  • Single-walled carbon nanotube single-walled carbon nanotube: SWNT
  • double-walled carbon nanotube double-walled carbon nanotube
  • VGCF vapor-grown carbon fiber
  • spur-growth CNT manufactured by the New Energy and Industrial Technology Development Organization
  • eDIPS-CNT manufactured by the New Energy and Industrial Technology Development Organization
  • SWNT series manufactured by Meijo Nano Carbon: product name
  • VGCF registered trademark
  • FloTube series manufactured by CNano Technology: product name
  • AMC manufactured by Ube Industries, Ltd.: trade name
  • NANOCYL NC7000 series manufactured by Nanocyl SA: trade name
  • Baytubes manufactured by Bayer: trade name
  • GRAPHISTRENGTH manufactured by Arkema: trade name
  • MWNT7 Hodogaya Chemical Industry Co., Ltd.: trade name
  • Hyperion CNT Hypeprion Catalysis International: trade name
  • Examples of the carbon material as the catalyst carrier in the cathode catalyst layer 103 of the present embodiment include activated carbon obtained by carbonizing and activating materials containing various carbon atoms, coke, natural graphite, artificial graphite, graphitized carbon, and the like. be done.
  • the metal mesh as the catalyst carrier in the cathode catalyst layer 103 of the present embodiment includes metal meshes of nickel, titanium, zirconium, etc., and metal meshes of zirconium are preferred.
  • Examples of the metal foam as the catalyst carrier in the cathode catalyst layer 103 of the present embodiment include metal foams such as aluminum, magnesium, titanium, zirconium, zinc, iron, tin, lead, and alloys containing these. , zirconium metal foams are preferred.
  • Metal oxides as catalyst carriers in the cathode catalyst layer 103 of the present embodiment include, for example, aluminum oxide, zirconium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, oxide Copper, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, silver oxide, tantalum oxide, tungsten oxide, osmium oxide, iridium oxide, indium oxide, cerium oxide, samarium oxide, platinum oxide, gold oxide, magnesium oxide or silica and the like, preferably aluminum oxide, iron oxide, copper oxide, zinc oxide, molybdenum oxide, tungsten oxide, cerium oxide, samarium oxide and silica; aluminum oxide, zinc oxide, molybdenum oxide, cerium oxide, samarium oxide and Silica is more preferred.
  • Examples of the composite oxide as the catalyst carrier in the cathode catalyst layer 103 of the present embodiment include silica-alumina, silica-magnesia, etc. Silica-alumina is preferred.
  • Polymer electrolytes as catalyst carriers in the cathode catalyst layer 103 of this embodiment include fluorine-based polymer electrolytes, hydrocarbon-based polymer electrolytes, anion-conducting electrolytes, and the like.
  • fluorine-based polymer electrolytes include fluorine-based sulfonic acid polymers such as DuPont's Nafion (registered trademark), Solvay's Aquivion (registered trademark), AGC's Flemion (registered trademark), and partially fluorine-based carbonization.
  • Hydrocarbon polymer electrolytes include, for example, sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • anion-conducting electrolyte Fumion (registered trademark) FAA-3-SOLUT-10 manufactured by Fumasep, A3ver.
  • AS-4 (A3ver.2 and AS-4 are described in, for example, the magazine "Hydrogen Energy System", Vo1.35, No.2, 2010, page 9.), and the electrolyte membrane described later
  • a cation exchange membrane hereinafter also referred to as a cation exchange membrane
  • Nafion registered trademark
  • Aquivion registered trademark
  • an anion exchange membrane hereinafter also referred to as an anion exchange membrane
  • Examples of the ionic liquid as the catalyst carrier in the cathode catalyst layer 103 of this embodiment include imidazolium salts, pyridinium salts, ammonium salts, phosphonium salts, pyrrolidinium salts, piperidinium salts, sulfonium salts, and the like.
  • imidazolium salts include formula (1): Those represented by are mentioned.
  • R 1a to R 5a may be the same or different, and may each be a hydrogen atom, a C 1 to C 10 alkyl group, an allyl group, or a vinyl group.
  • anion X a- in formula (1) include fluorine ion, chloride ion, bromide ion, iodine ion, tetrafluoroborate, trifluoro(trifluoromethyl)borate, dimethylphosphate ion, diethyl Phosphate ion, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, trifluoroacetate, methylsulfate, ethylsulfate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, hydrogen sulfate ion, etc. mentioned.
  • cations in formula (1) include 1-allyl-3-methylimidazolium ion, 3-ethyl-1-vinylimidazolium ion, 1-methylimidazolium ion, and 1-ethylimidazolium ion.
  • pyridinium salts include formula (2): Those represented by are mentioned.
  • R 1b to R 6b may be the same or different, and each includes a hydrogen atom, a hydroxymethyl group, or a C 1 to C 6 alkyl group.
  • examples of the anion X a- in formula (2) include the same ones as in formula (1) above.
  • cations in formula (2) include 1-butyl-3-methylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-butyl-pyridinium ion, 1-ethyl-3-methylpyridinium ion. and salts of pyridinium ions such as 1-ethylpyridinium ion, 1-ethyl-3-(hydroxymethyl)pyridinium ion, and X 1 - in formula (1) above.
  • ammonium salts include formula (3): Those represented by are mentioned.
  • R 1c to R 4c may be the same or different, and are each a hydrogen atom, a methoxyethyl group, a phenylethyl group, a methoxypropyl group, a cyclohexyl group, or a C 1 to C 8 alkyl group. groups. Further, examples of the anion X a- in the formula (3) include the same ones as in the formula (1).
  • cations in formula (3) include triethylpentylammonium ion, diethyl(methyl)propylammonium ion, methyltri-n-octylammonium ion, trimethylpropylammonium ion, cyclohexyltrimethylammonium ion, diethyl(2- methoxyethyl)-methylammonium ion, ethyl(2-methoxyethyl)-dimethylammonium ion, ethyl(3-methoxypropyl)dimethyl-ammonium ion, ethyl(dimethyl)(2-phenylethyl)-ammonium ion, tetramethylammonium ion , tetraethylammonium ion, triethylpentylammonium ion, tetra-n-butylammonium ion, diethylp
  • phosphonium salts include formula (4): Those represented by are mentioned.
  • R 1d to R 4d may be the same or different, and each includes a hydrogen atom, a methoxyethyl group, or a C 1 to C 10 alkyl group. Further, examples of the anion X a- in the formula (4) include the same ones as in the formula (1).
  • cations in formula (4) include tributylmethylphosphonium ion, tetrabutylphosphonium ion, trihexyl(tetradecyl)phosphonium ion, trihexyl(ethyl)phosphonium ion, tributyl(2-methoxyethyl)-phosphonium ion, and the like. and a salt of X a- in the above formula (1).
  • pyrrolidinium salts include formula (5): Those represented by are mentioned.
  • R 1e to R 2e may be the same or different, and each includes a hydrogen atom, an allyl group, a methoxyethyl group, or a C 1 to C 8 alkyl group.
  • X a- which is an anion in formula (5), includes the same ones as in formula (1) above.
  • cations in formula (5) include, for example, 1-allyl-1-methylpyrrolidinium ion, 1-(2-methoxyethyl)-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrroli Pyrrolidinium ion such as dinium ion, 1-methyl-1-propylpyrrolidinium ion, 1-octyl-1-methylpyrrolidinium ion, 1-hexyl-1-methylpyrrolidinium ion and X a- in the above formula (1) and salt.
  • piperidinium salts include formula (6): Those represented by are mentioned.
  • R 1f to R 2f may be the same or different, and each includes a hydrogen atom or a C 1 to C 6 alkyl group. Further, examples of the anion X a- in the formula (6) include the same ones as in the formula (1).
  • cations in formula (6) include piperidinium ions such as 1-butyl-1-methylpiperidinium ion and 1-methyl-1-propylpiperidinium ion and X a in formula (1). - and salts.
  • sulfonium salts include formula (7): Those represented by are mentioned.
  • R 1g to R 3g may be the same or different, and each includes a hydrogen atom or a C 1 to C 4 alkyl group. Further, examples of the anion X a- in the formula (7) include the same ones as in the formula (1).
  • cations in formula (7) include salts of sulfonium ions such as triethylsulfonium ion and trisulfonium ion with X a- in formula (1).
  • ionic liquid 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3- Methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium iodide , 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorotrifluorophosphate, 1-butyl-3-methylimidazolium trifluoro(trifluoromethyl)borate, 1-butyl-2,3-dimethylimidazolium lithium trifluoromethanesulfonate, 1-butyl-3-methylimid
  • the catalyst carrier of the present embodiment carbon black, Ketjenblack, Ketjenblack EC, Nafion (registered trademark), aluminum oxide, zinc oxide, molybdenum oxide, cerium oxide, samarium oxide, silica, silica-alumina , 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, 1-butyl-3-methylimidazolium tris(pentafluoroethyl) Trifluorotrifluorophosphate is preferred.
  • One of these catalyst carriers may be used alone, or two or more may be used in combination.
  • carbon black and aluminum oxide in combination, carbon black and zinc oxide in combination, carbon black and molybdenum oxide, carbon black and cerium oxide, carbon black and samarium oxide, carbon black and silica, Ketjenblack EC and aluminum oxide, Ketjenblack EC and zinc oxide Ketjenblack EC and molybdenum oxide, Ketjenblack EC and cerium oxide, Ketjenblack EC and samarium oxide, and Ketjenblack EC and silica are preferable.
  • the reaction field forming material in the ammonia production method of the present embodiment is selected from the group consisting of reaction gas, electrons and ions in the cathode catalyst layer, the anode catalyst layer, or both the cathode catalyst layer and the anode catalyst layer.
  • the complex as a catalyst may be used in a form supported on a reaction field forming material, and those having these forms are also referred to as a catalyst body in this specification. Describe.
  • reaction field forming materials include calcined carbon, calcined nitrogen, calcined nitrogen carbon, rare earth metal-carbon composites, and hydrophilic polymers.
  • Rare earth metal-carbon-based combined body is obtained by performing a reaction of firing a conventional conductive carbon material raw material and an aromatic compound having a phenolic hydroxyl group to obtain a carbon fired body, then combining the fired body and the rare earth. It is a complex of a rare earth metal ion and the above fired product, which can be obtained by a reaction to obtain a complex with a metal ion or by firing.
  • a product obtained by firing a mixture of an aromatic compound having a phenolic hydroxyl group and a conductive carbon material raw material is defined as a "carbon fired body".
  • a complex of the fired body and the rare earth metal ion, in which the rare earth metal ion forms a complex with the substituent or structure of the fired body is defined as a "rare earth metal-carbon-based bond".
  • a product obtained by firing a mixture of a nitrogen-containing compound component and a conductive carbon material raw material is defined as a "nitrogen fired body”.
  • a "nitrogen-carbon calcined body” is defined as a calcined mixture of a nitrogen-containing compound component, an aromatic compound having a phenolic hydroxyl group, and a conductive carbon material raw material.
  • the carbon calcined body, the nitrogen calcined body, and the nitrogen carbon calcined body are sometimes referred to as calcined bodies.
  • aromatic compounds having a phenolic hydroxyl group in the fired body of the present embodiment include monocyclic or condensed polycyclic aromatic compounds having one or more phenolic hydroxyl groups.
  • 1 to 6 phenols which are monocyclic aromatic compounds and have 1 to 6 phenolic hydroxyl groups, can be mentioned.
  • Phenols which are monocyclic aromatic compounds and have one phenolic hydroxyl group include, for example, phenol, ethylphenol, pt-butylphenol, o-cresol, m-cresol, p-cresol, 2,3 -xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, thymol, mesitol, butoidcumenol, 2,6-di-t-butyl-p-cresol, pentamethylphenol, o- Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, capicol, o-allylphenol, anol, diethylstilbestrol, p-(methylthio)phenol, o-aminophenol, m-aminophenol, p-aminophenol, o -(methylamino)phenol, m-(methyla
  • Phenols that are monocyclic aromatic compounds and have two phenolic hydroxyl groups include, for example, catechol, resorcinol, hydroquinone, 3,4-toluenediol, 2,5-toluenediol, and 3,5-toluenediol. , 2,4-toluenediol, urushiol, p-xylene-2,6-diol, m-xylene-4,6-diol, p-xylene-2,5-diol, 2-isopropyl-5-methylhydroquinone, etc. is mentioned.
  • Phenols which are monocyclic aromatic compounds and have three phenolic hydroxyl groups include, for example, pyrogallol, 1,2,4-benzenetriol, phloroglycinol, 2-methylphloroglycinol, m-xylene- 2,4,6-triol, 2,4,6-trimethylphlologlycinol, and the like.
  • Phenols which are monocyclic aromatic compounds and have four phenolic hydroxyl groups include, for example, 1,2,3,5-benzenetetraol and 1,2,4,5-benzenetetraol. be done. Examples of phenols that are monocyclic aromatic compounds and have six phenolic hydroxyl groups include hexahydroxybenzene.
  • the monocyclic aromatic compound having a phenolic hydroxyl group 3 to 6 phenols having 3 to 6 phenolic hydroxyl groups are more preferable, and the monocyclic aromatic compound has 3 phenolic hydroxyl groups.
  • Phenols having the following formula (I) are more preferable, and phloroglucinol represented by the following formula (I) is particularly preferable.
  • Condensed polycyclic aromatic compounds include naphthalene, azulene, heptalene, biphenylene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, aceanthrylene, triphenylene, pyrene, chrysene, tetracene, perylene, pentacene, picene, coronene, and the like. and naphthalene, anthracene and triphenylene are preferred.
  • Condensed polycyclic aromatic compounds having a phenolic hydroxyl group include, for example, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,3,8-trihydroxynaphthalene, 9,10-anthracene or ellagic acid, 2,3,6,7,10,11-hexahydroxytriphenylene and the like, preferably 2,6-dihydroxynaphthalene, 1,3,8-trihydroxynaphthalene, 9,10-anthracene and ellagic acid; ,3,6,7,10,11-hexahydroxytriphenylene, more preferably ellagic acid represented by the following formula (II), 2,
  • An aromatic compound having a phenolic hydroxyl group may be used alone or in combination of two or more.
  • the aromatic compound having a phenolic hydroxyl group, whether monocyclic or condensed polycyclic, preferably has 3 or more phenolic hydroxyl groups, and preferably has 3 to 6 phenolic hydroxyl groups. more preferred. This is because it is possible to form a three-dimensional polymer as described later.
  • Carbon black, carbon nanotubes, graphene nanoplatelets, and the like can be used as the conductive carbon material raw material (hereinafter also referred to as “carbon material raw material”) in the fired body of the present embodiment. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Examples of carbon black include ketjen black, ketjen black EC, channel black, oil furnace black, vulcan, furnace black, thermal black, acetylene black, lamp black, graphitized black, oxidized black, etc., which have good conductivity. Therefore, acetylene black, Ketjenblack, and Ketjenblack EC are preferred, and Ketjenblack and Ketjenblack EC are more preferred.
  • Carbon black may be used alone, or two or more types may be used in combination. Carbon black may be surface-treated. Specific examples of carbon black include Denka Black (manufactured by Denka Co., Ltd.); ); Asahi HS-500, Asahi #8, Asahi #15, Asahi #15HS, Asahi #22K, Asahi Thermal, Asahi #35, Asahi #50, Asahi #50U, Asahi #50HG, Asahi #51, Asahi #52, Asahi #55, Asahi #60U, Asahi #60HN, Asahi #65, Asahi F-200GS, Asahi #70, Asahi #80, Asahi #95, Asahi AX-015, Asahi #15HS (manufactured by Asahi Carbon); Ketjen Black EC300J, Carbon ECP, Ketjenblack EC600JD
  • carbon nanotubes for example, vapor growth, catalytic vapor growth, catalytic chemical vapor deposition, chemical vapor deposition, super multiplication, catalytic carbon deposition, arc discharge, laser evaporation, etc.
  • the resulting single-walled nanotubes and multi-walled carbon nanotubes can be exemplified, and these can take any form such as a needle-like, coil-like, or tube-like form.
  • the carbon nanotube tube it has a cylindrical shape by winding one sheet of graphite with a carbon hexagonal network surface, and it is a multi-wall carbon nanotube wound in three or more layers (multi-wall carbon nanotube), one of graphite.
  • Single-walled carbon nanotube (single-walled carbon nanotube: SWNT), double-walled carbon nanotube (double-walled carbon nanotube: DWNT), vapor-grown carbon fiber (VGCF, Showa Denkosha) (registered trademark) of the company).
  • spur-growth CNT manufactured by the New Energy and Industrial Technology Development Organization of Japan
  • eDIPS-CNT manufactured by the New Energy and Industrial Technology Development Organization of the National Research and Development Agency
  • SWNT series Lijo Nano Carbon: trade name
  • VGCF registered trademark
  • VGCF-H registered trademark
  • VGCF-X manufactured by Showa Denko Co., Ltd.: registered trademark
  • FloTube series manufactured by CNano Technology: trade name
  • AMC manufactured by Ube Industries, Ltd.: trade name
  • NANOCYL NC7000 series manufactured by Nanocyl S.A.: trade name
  • Baytubes manufactured by Bayer: trade name
  • GRAPHISTRENGTH manufactured by Arkema: trade name
  • MWNT7 Hodogaya Chemical Industry Co., Ltd.: trade name
  • Hyperion CNT Hyperion CNT
  • Carbon nanotubes may be used singly or in combination of two or more. Carbon nanotubes may be surface-treated. Furthermore, carbon black and carbon nanotubes may be used in combination.
  • the conductive carbon material raw material is preferably at least one selected from the group consisting of Ketjenblack, Ketjenblack EC, and carbon nanotubes.
  • the conductive carbon material raw material is selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonyl group, a formyl group, a sulfonic acid group, an oxysulfonic acid group, a carboxylic acid anhydride structure, a chromene structure, a lactone structure, an ester structure and an ether structure. It is preferable to have at least one selected substituent, and at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, a carboxylic anhydride structure, a lactone structure, an ester structure and an ether structure. and more preferably at least one substituent selected from the group consisting of a hydroxyl group, a lactone structure and an ester structure.
  • the nitrogen-containing compound component in the fired body of the present embodiment includes a nitrogen-containing compound, a salt of a nitrogen-containing compound, a resin containing a structural unit derived from a nitrogen-containing compound, a resin containing a structural unit derived from a nitrogen-containing compound, and an inorganic compound.
  • a complex of These may be used individually by 1 type, or may be used in combination of 2 or more types.
  • Nitrogen-containing compounds include urea, aromatic urea compounds, guanidine compounds, triazine-based heterocyclic compounds, and nitrogen-containing condensed ring compounds.
  • aromatic urea compounds include phenylurea, benzylurea, N-ethyl-N'-phenylurea, p-ethoxyphenylurea, N,N'-diphenylurea, N,N-diphenylurea, tetraphenylurea, and benzoyl urea.
  • guanidine compounds include guanidine, methylguanidine, nitroguanidine, aminoguanidine, biguanide, dicyandiamide, carbamoylguanidine, glycocyamine, creatine, N,N'-diphenylguanidine and triphenylguanidine. is preferred.
  • triazine heterocyclic compounds examples include 1,3,5-triazine, cyanuric chloride, cyanuric acid, trimethyl cyanurate, methyl isocyanurate, ethyl isocyanurate, melamine, melem, melam, ammeline, ammelide, benzoguanamine, and methylguanamine.
  • 1,3,5-trimethyltriazine, 1,3,5-triphenyltriazine, amelin, ameride, thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, or diaminoisopropoxytriazine, and melamine is preferred.
  • Nitrogen-containing condensed ring compounds include, for example, purine, xanthine, caffeine, uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, 3-methyluric acid, and 7-methyluric acid. etc.
  • the nitrogen-containing compounds may be used singly or in combination of two or more.
  • the nitrogen-containing compound preferably has 3 or more functional groups. This is because it is possible to form a three-dimensional polymer as described later.
  • Melamine resins are examples of resins containing structural units derived from nitrogen-containing compounds.
  • Melamine resin is a polycondensation product of melamine and its derivatives, which are nitrogen-containing compounds, and aldehyde compounds. can be used. These melamine and its derivatives and aldehyde compounds may be used alone or in combination of two or more.
  • melamine resins can also be used.
  • Commercial product names include, for example, Cymel 202, Cymel 203, Cymel 204, Cymel 211, Cymel 212, Cymel 238, Cymel 251, Cymel 253, Cymel 254, Cymel 303, Cymel 323, Cymel 324, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 380, Cymel 385, Cymel 1156, Cymel 1158, Cymel 1116, Cymel 1130 (manufactured by Allnex Japan Co., Ltd.); Regimin 735, Regimin 740, Regimin 741, Regimin 745, Regimin 746, Regimin 747 (manufactured by Monsanto); Uvan 120, Uvan 20HS, Uvan 20SE, Uvan 2021, Uvan 2028, Uvan 28-60 (manufactured by Mitsui Chemicals, Inc.); Sumimar M55, Sumimar M30W, Sumimar M50W (manufactured by Sumi
  • the acid that forms a salt with the nitrogen-containing compound is not particularly limited, but examples include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, sulfamic acid, nitric acid, perchloric acid, carbonic acid, and hydrogen iodide. acid, hydrobromic acid, thiocyanic acid, and the like.
  • Salts of guanidine compounds of nitrogen-containing compounds include guanidine carbonate, guanidine phosphate, guanidine thiocyanate, and aminoguanidine hydrochloride, preferably guanidine carbonate.
  • Salts of cyanuric acid or isocyanuric acid, which are nitrogen-containing compounds also include melamine cyanurate and melamine isocyanurate.
  • Melamine cyanurate or melamine isocyanurate is an organic salt of cyanuric acid or isocyanuric acid, which is an acidic compound, and a triazine compound, which is a basic compound.
  • a salt having the composition of These can be produced by a known method. For example, a mixture of melamine and cyanuric acid or isocyanuric acid is suspended in water and mixed to form a salt of the two, and the slurry is filtered and dried to obtain a powder.
  • salts of nitrogen-containing compounds include salts of basic compounds melamine, melam and melem with polyphosphoric acid. is 31 to 46%, and melem is 8 to 17%. ) and the like. Salts of nitrogen-containing compounds may be used singly or in combination of two or more.
  • crosslinked melamine resin microparticles are composite spherical particles composed of a crosslinked melamine resin as a resin containing a structural unit derived from a nitrogen-containing compound and silica as an inorganic compound.
  • Examples of commercial products of crosslinked melamine resin fine particles include "Optobeads (registered trademark) 500SL (average particle size 0.5 ⁇ m)" and “Optobeads (registered trademark) 500S (average particle size 0.5 ⁇ m).
  • Beads 500SL and Optobeads® 2000M A composite of a resin containing a constitutional unit derived from a nitrogen-containing compound and an inorganic compound may be used singly or in combination of two or more.
  • the nitrogen-containing compound component is at least one selected from the group consisting of guanidine carbonate, melamine, melamine cyanurate, composite spherical particles composed of a crosslinked melamine resin and silica, and melamine, melam, and salts of melem and polyphosphoric acid. is preferred, and at least one selected from the group consisting of guanidine carbonate and melamine is more preferred.
  • a method for manufacturing the sintered body of this embodiment will be described.
  • a calcined carbon body is obtained by calcining a mixture of an aromatic compound having a phenolic hydroxyl group and a carbon material raw material.
  • a nitrogen sintered body is obtained by sintering a mixture of a nitrogen-containing compound component and a carbon material raw material.
  • a nitrogen-carbon sintered body is obtained by sintering a mixture of a nitrogen-containing compound-based component, an aromatic compound having a phenolic hydroxyl group, and a carbon material raw material.
  • the firing temperature is a temperature at which the nitrogen-containing compound component and any aromatic compound having a phenolic hydroxyl group can be polymerized or carbonized. ⁇ 600°C is even more preferred. Firing is carried out at a firing temperature, preferably for 1 to 10 hours, more preferably for 1 to 5 hours. Firing can be performed under air or under an inert gas, and examples of the inert gas include nitrogen and argon.
  • the structure of the sintered body will be explained.
  • the nitrogen-containing compound-based component as the starting material and the aromatic compound having a phenolic hydroxyl group as the preferred starting material may be contained in the sintered body as it is in the core structure of the starting material.
  • at least part of the raw material nitrogen-containing compound component and the preferred raw material aromatic compound having a phenolic hydroxyl group may be contained in the fired product as respective three-dimensional polymers.
  • the raw material nitrogen-containing compound component and the preferred raw material aromatic compound having a phenolic hydroxyl group undergo thermal condensation reaction and thermal polymerization reaction by firing to form a three-dimensional polymer of an aromatic compound having a phenolic hydroxyl group, and It is considered that a three-dimensional polymer of the nitrogen-containing compound constituting the nitrogen-containing compound component of the raw material may be formed.
  • the aromatic compound having a phenolic hydroxyl group as a raw material has three or more phenolic hydroxyl groups and contains nitrogen-containing compound components as a raw material.
  • the nitrogen compound has 3 or more functional groups.
  • a three-dimensional polymer of an aromatic compound having a phenolic hydroxyl group is represented by the following formula (a), for example, when phloroglucinol represented by the following formula (I) is used as a starting material.
  • a three-dimensional polymer of a nitrogen-containing compound is, for example, melam represented by the following formula (ii), which is a deammonification condensate, by baking melamine (i) as a raw material while desorbing ammonia.
  • melam represented by the following formula (ii) which is a deammonification condensate
  • a compound represented by the following formula (iv) or formula (v) a melon represented by the following formula (vi), formula (vii) or formula (viii), etc. be.
  • Examples of the three-dimensional polymer of the nitrogen-containing compound include a structure in which a large number of structures such as (i) to (viii) are linked, and is represented by the following formula (ix), for example.
  • g-C3N4 which is graphitic carbon nitride represented by the following formula (x)
  • Non-patent document A Kogyo Kagaku Zasshi 1963, Vol. 66, No. 6, pp. 804-809
  • Non-patent document B Chem.Eur.J. 2007, Vol. 13, pp. 4969-4980
  • the nitrogen-containing compound component of the raw material and the aromatic compound having a phenolic hydroxyl group of the preferred raw material are either contained as they are in the core structure of the raw material, or as a three-dimensional polymer. It is believed that whether or not this depends on the conditions such as the temperature and time of calcination, the nitrogen-containing compound component of the raw material, and the structure of the aromatic compound having a phenolic hydroxyl group, which is the preferred raw material.
  • the three-dimensional polymer of formula (a) and the formula ( ix) and the three-dimensional polymer are considered to be entangled with each other.
  • the metal species of the rare earth metal ion in the rare earth metal-carbon-based bond which is the reaction field forming material of the present embodiment, includes scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.
  • holmium, erbium, thulium, ytterbium or lutetium preferably scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and ytterbium, scandium, yttrium, lanthanum, cerium, samarium, Europium and ytterbium are more preferred.
  • a complex is formed between the substituent of the fired body and the rare earth metal ion.
  • the complex structure between the substituent of the fired body and the rare earth metal ion the complex structure of the substituent derived from the surface of the carbon material raw material and the carbon deficiency part and the rare earth metal ion and the complex structure derived from the aromatic compound having a phenolic hydroxyl group
  • a complex structure of a hydroxyl group and a rare earth metal ion can be mentioned. These may be either one of the complex structures or both complex structures.
  • the complex structure between the substituent derived from the surface of the carbon material raw material and the carbon deficiency portion and the rare earth metal ion includes a hydroxyl group, a carboxyl group, a carbonyl group, a formyl group, a sulfonic acid group, an oxysulfonic acid group derived from the carbon material raw material, At least one substituent selected from the group consisting of a carboxylic anhydride structure, a chromene structure, a lactone structure, an ester structure and an ether structure forms a bond between a monovalent anion formally deprotonated and a rare earth metal ion. mentioned.
  • the rare earth metal ion forms a complex structure via —O— with the surface of the carbon material raw material and the substituents on the carbon-deficient portion. More preferably, the rare earth metal ion forms one or more cyclic structures, ie, a chelate ring, with the surface of the carbon material raw material via —O— for the reason of increasing its stability. are mentioned.
  • a partial structure represented by the following formula (a) formed by firing an aromatic compound having a phenolic hydroxyl group and a rare earth metal A complex structure with an ion, for example, a partial structure represented by formula (b) can be mentioned.
  • Ln in the formula (b) represents a rare earth metal and includes the same metal species as the rare earth metal ion.
  • a method for producing the rare earth metal-carbon-based composite of this embodiment will be described.
  • ⁇ Rare earth metal-carbon-based composite manufacturing method A> A rare earth metal-carbon-based bond in which the rare earth metal ion forms a complex structure with the substituents of the sintered body can be produced by step 1A. From the viewpoint of durability, it is preferable to perform step 2A after step 1A.
  • step 1A the fired body of the present invention and a rare earth metal compound are reacted to form a complex between the rare earth metal ion and the substituent of the fired body of the present invention, and the complex of the fired body and the rare earth metal ion is a rare earth.
  • a metal-carbon composite is obtained.
  • the reaction between the fired body and the rare earth metal compound is performed by reacting the fired body and the rare earth metal compound in a solvent.
  • Substituents of the fired body used in the reaction of step 1A include hydroxyl group, carboxyl group, carbonyl group, formyl group, sulfonic acid group, oxysulfonic acid group, carboxylic acid anhydride structure, chromene structure, lactone structure, ester structure and ether It is preferably at least one selected from the group consisting of structures, and at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, a carboxylic anhydride structure, a lactone structure, an ester structure and an ether structure. It more preferably has a substituent, and more preferably at least one selected from the group consisting of a hydroxyl group, a lactone structure, an ester structure and an ether structure.
  • rare earth metal alkoxide compounds include rare earth metal triisopropoxide.
  • rare earth metal triisopropoxides include scandium triisopropoxide, yttrium triisopropoxide, lanthanum triisopropoxide, cerium triisopropoxide, praseodymium triisopropoxide, neodymium triisopropoxide, and promethium triisopropoxide.
  • rare earth metal acetylacetonato compounds include tris(acetylacetonato)scandium(III), tris(acetylacetonato)yttrium(III), tris(acetylacetonato)lanthanum(III), tris(acetylacetonato) ) Cerium(III), Tris(acetylacetonato)neodymium(III), Tris(acetylacetonato)promethium(III), Tris(acetylacetonato)samarium(III), Tris(acetylacetonato)eurobium(III), Tris(acetylacetonato)gadolinium (III), Tris(acetylacetonato)terbium(III), Tris(acetylacetonato)dysprosium(III), Tris(acetylacetonato)holmium(III), Tris(acetylacetonato)
  • Step 1 is, for example, sodium hydride, lithium hydride, sodium hydroxide, 1,8-diazabicyclo-5,4,0-undec-7-ene (DBU), trimethylamine, triethylamine, tripropylamine, N-ethyl It can also be carried out in the presence of methylbutylamine, tributylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, tribenzylamine and the like. Among these, sodium hydride and lithium hydride are preferred.
  • the solvent used in step 1A may be any non-aqueous solvent capable of dispersing the fired body and dissolving or dispersing the rare earth metal compound.
  • 1,3-Propanesultone which is the target of the reaction, can also serve as a solvent.
  • Toluene, tetrahydrofuran, dimethylsulfoxide, N,N-dimethylformamide and 1,3-propanesultone are preferred, and tetrahydrofuran is more preferred.
  • the reaction temperature in step 1A is preferably -10 to 200°C, more preferably 10 to 160°C, still more preferably 15 to 140°C.
  • the reaction time of step 1A is preferably 1 to 500 hours, more preferably 2 to 300 hours, even more preferably 5 to 150 hours.
  • step 2A the rare earth metal-carbon composite, which is a complex of the sintered body obtained in step 1A and the rare earth metal, is washed with acid and water. Before being used in a fuel cell device, the complex that has undergone step 2A is washed to eliminate reacting substituents and impurities. Excellent.
  • the acid used in step 2A include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, sulfurous acid, nitrous acid, and phosphoric acid, and organic acids such as acetic acid, lactic acid, oxalic acid, citric acid, and formic acid. Sulfuric acid is preferable because it can be used for fuel cell devices and impurities are less likely to remain.
  • ⁇ Rare earth metal-carbon-based composite manufacturing method B> A rare earth metal-carbon-based bond in which rare earth metal ions form a complex structure with the substituents of the fired body can be produced by step 1B, and step 2B may be performed after step 1B, if necessary. .
  • step 1B a mixture of the fired body of the present invention and a rare earth metal compound is fired to obtain a complex of the fired body and the rare earth metal ion in which a complex structure of the rare earth metal ion and the substituent of the fired body is formed.
  • Substituents of the fired body used in the reaction of step 1B include hydroxyl group, carboxyl group, carbonyl group, formyl group, sulfonic acid group, oxysulfonic acid group, carboxylic acid anhydride structure, chromene structure, lactone structure, ester structure and ether It is preferably at least one selected from the group consisting of structures, and at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, a carboxylic anhydride structure, a lactone structure and an ester structure. More preferably, it has at least one selected from the group consisting of a hydroxyl group, a lactone structure, an ester structure and an ether structure.
  • Examples of the rare earth metal compound used in Step 1B include the same compounds as those described in Step 1A.
  • the rare earth metal compound used in step 1B Ce( CH3CO2 ) 3 - xH2O , Ce( C5H7O2 ) 3 - xH2O , Eu ( CH3CO2 ) 3 - xH2O , Gd( CH3CO2 ) 3 - xH2O , Gd ( C5H7O2 ) 3 - xH2O , La ( CH3CO2 ) 3 - xH2O , La ( C5H7O2 ) 3.xH2O , Tb ( CH3CO2 ) 3 - xH2O , Yb ( C2H3O2 ) 3-4H2O , cerium triisopropoxide, samarium triisopropoxide, At least one selected from the group consisting of tris(acetylacetonato)cerium(III) and
  • the firing temperature in step 1B is preferably 100-1000°C, more preferably 150-600°C, and even more preferably 200-500°C.
  • the firing time in step 1B is preferably 1 to 500 hours, more preferably 2 to 300 hours, and even more preferably 5 to 150 hours.
  • the atmosphere for firing in step 1B can be performed under the atmosphere or under an inert gas.
  • the atmosphere include air, and examples of the inert gas include nitrogen and argon.
  • the firing atmosphere is preferably under an inert gas, and the inert gas is preferably nitrogen.
  • the hydrophilic polymer is described below.
  • the hydrophilic polymer in the ammonia production method of the present embodiment exhibits hydrophilicity by containing a polar or charged functional group in the polymer, and the functional group having a strong interaction with water is added to the polymer.
  • I have many inside.
  • Examples of functional groups that have strong interactions with water include ionic groups, hydroxy groups, amino groups, amide groups, ether groups, and the like.
  • the weight average molecular weight measured by gel permeation chromatography is 10,000 to 3,000,000, preferably 20,000 to 2,000,000, and 30,000 to 1,500,000. more preferred.
  • hydrophilic polymers examples include polyvinyl alcohol, polyacrylamide, polyethyleneimine, polyacrylic acid, polyvinylpyrrolidone, polypyridine, poly(4-vinylpyridine), poly(2-vinylpyridine), poly(4-vinylpyridine- co-styrene) and the like, and these may be used alone or in combination of two or more.
  • polyvinyl alcohol, polyvinylpyrrolidone, poly(4-vinylpyridine) and poly(2-vinylpyridine) are preferred, and polyvinyl alcohol or polyvinylpyrrolidone is more preferred.
  • a mixture of hydrophilic polymer and iodine can be used as an example of preparing the reaction field forming material.
  • iodine a mixture of hydrophilic polymer and iodine (reagent)
  • povidone-iodine which is a complex of polyvinylpyrrolidone and iodine, can also be used.
  • the electron conductor in the cathode catalyst layer 103 of the present embodiment is not particularly limited as long as it conducts electrons, and may serve as a catalyst carrier.
  • examples thereof include carbon black, carbon nanotubes, carbon materials, metal meshes, metal foams, and the like, and may be used singly or in combination of two or more.
  • Carbon black, carbon nanotubes, carbon materials, metal Specific examples of the mesh and metal foam are the same as those described in the description of the catalyst carrier herein.
  • the electronic conductor of the present embodiment carbon black, Ketjenblack, Ketjenblack EC, nickel metal mesh, titanium metal mesh and metal foam are used because of their high specific surface area and excellent electronic conductivity.
  • IFPC40 and IFPC40-II manufactured by Ishifuku Metal Industry Co., Ltd., TEC10E40E, TEC10E50E, TEC10E60TPM, TEC10E70TPM, TEC10V30E, TEC10V40E, TEC10V50E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., Johnson Matthey Fuels. ⁇ HiSPEC4000 manufactured by Japan Co., Ltd., etc. can be mentioned.
  • the electrolyte in the cathode catalyst layer 103 of the embodiment is not particularly limited as long as it is responsible for ion conduction, and examples thereof include cation-exchange electrolytes and anion-exchange electrolytes.
  • cation exchange type electrolytes include fluorine-based polymer electrolytes and hydrocarbon-based polymer electrolytes.
  • fluorine-based polymer electrolytes include fluorine-based sulfonic acid polymers such as DuPont's Nafion (registered trademark), Solvay's Aquivion (registered trademark), AGC's Flemion (registered trademark), and partially fluorine-based carbonization. Examples include hydrogen-based sulfonic acid polymers.
  • Hydrocarbon polymer electrolytes include, for example, sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • anion-exchange electrolytes include FuMA-Tech's Fumion (registered trademark) FAA-3-SOLUT-10 and Tokuyama's A3ver. 2, AS-4 (A3ver.2 and AS-4 are described, for example, in the magazine "Hydrogen Energy System", Vol. 1.35, No. 2, 2010, page 9).
  • electrolyte in the cathode catalyst layer 103 of the present embodiment when a cation exchange membrane is used as the electrolyte membrane to be described later, an electrolyte that conducts at least one of protons and hydroxonium ions is preferable. trademark) and Aquivion® are preferred.
  • an anion exchange membrane is used as the electrolyte membrane to be described later, it is preferable to conduct hydroxide ions, and FAA-3-SOLUT-10 and AS-4 are preferable.
  • the gas diffusion layer in the cathode catalyst layer 103 of this embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and electrolyte diffusion. Examples thereof include carbon paper, carbon felt, carbon cloth, and the like.
  • the cathode catalyst layer 103 including a complex, a cathode solid catalyst, or a catalyst body that is a complex and a cathode solid catalyst, and including a gas diffusion layer may be referred to as a gas diffusion electrode 133 .
  • Examples of carbon paper include Toray's TGP-H-060, TGP-H-090, TGP-H-120, TGP-H-060H, TGP-H-090H, TGP-H-120H, Electrochem's EC-TP1-030T, EC-TP1-060T, EC-TP1-090T, EC-TP1-120T, SIGRACET 22BB, 28BC, 36BB, 39BB and the like.
  • Examples of the carbon cloth include EC-CC1-060, EC-CC1-060T, and EC-CCC-060 manufactured by Electrochem Corporation, Torayca (registered trademark) cloth manufactured by Toray Industries, Inc., and CO6142, CO6151B, CO6343, CO6343B, and CO6347B. , CO6644B, CO1302, CO1303, CO5642, CO7354, CO7359B, CK6244C, CK6273C, CK6261C and the like.
  • Examples of carbon felt include H1410 and H2415 manufactured by Freudenberg.
  • TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H, and EC-TP1-060T are preferable for the gas diffusion layer in the cathode catalyst layer 103 of this embodiment.
  • the ion source arranged in the electrolytic device includes, for example, the electrolyte membrane 102 arranged beside the cathode catalyst layer 103, the electrolytic solution contained in the electrolyte membrane, and the cathode catalyst layer.
  • the electrolytic solution in the electrolytic solution tank arranged beside 103 is exemplified, and the electrolytic solution is a solution containing an electrolyte, and can supply ions, which are raw materials for producing ammonia, to the catalyst body of the cathode catalyst layer.
  • the ion source is preferably capable of supplying at least one of protons and hydroxonium ions, and the ion source in which the catalyst is placed is not particularly limited.
  • the environment is alkaline, one that can supply hydroxide ions is preferred, and these ion sources may be used singly or in combination of two or more.
  • solutions in the electrolytic solution in the method for producing ammonia of the present embodiment include water, ionic liquids, methanol, isopropyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, Diethylamine, hexamethylphosphonic acid triamide, acetic acid, acetonitrile, methylene chloride, trifluoroethanol, nitromethane, sulfolane, pyridine, tetrahydrofuran, dimethoxyethane, propylene carbonate, etc., water and ionic liquids are preferred.
  • Examples of the ionic liquid as a solution in the electrolytic solution in the ammonia production method of the present embodiment include imidazolium salts, pyridinium salts, ammonium salts, phosphonium salts, pyrrolidinium salts, piperidinium salts, sulfonium salts, and the like. mentioned.
  • an acid or a base to the ionic liquid as a solution in the electrolytic solution in the ammonia production method of the present embodiment, and when using a cation exchange membrane as the electrolyte membrane described later, an acid can be added.
  • an acid can be added.
  • a base specifically sodium hydroxide, potassium hydroxide etc.
  • Preferred ionic liquids to be added with acid or base are 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorotrifluorophosphate.
  • Examples of the electrolyte contained in the electrolytic solution in the method for producing ammonia of the present embodiment include protons, hydronium ions, lithium ions, sodium ions, potassium ions, imidazolium ions, pyridinium ions, ammonium ions, phosphonium ions, pylori cations such as dinium ion, piperidinium ion, or sulfonium ion, or cations in which a plurality of such cations are combined; ) borate, dimethyl phosphate ion, diethyl phosphate ion, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, Anions such as perchlorate ions, hydrogensulfate ions, sulfate
  • imidazolium ions, pyridinium ions, ammonium ions, phosphonium ions, pyrrolidinium ions, piperidinium ions and sulfonium ions as electrolytes contained in the electrolytic solution in the method for producing ammonia of the present embodiment are represented by the above formula Examples include cations described in (1) to formula (7).
  • the cation that is the electrolyte contained in the electrolytic solution in the method for producing ammonia of the present embodiment is preferably proton, hydronium ion, imidazolium ion, pyrrolidinium ion, and the anion that is the electrolyte is hydroxide ion, peroxide Chlorate ion, hydrogen sulfate ion and sulfate ion are preferred.
  • Catholyte electrolyte 106 used in cathode electrolyte tank 105 of the present embodiment is preferably water, aqueous sulfuric acid solution, 1-butyl-3-methyl Imidazolium bis(trifluoromethanesulfonyl) imides may be mentioned, and one kind may be used alone or two or more kinds may be used in combination.
  • an anion exchange membrane is used as the electrolyte membrane to be described later, specific examples include water, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution.
  • Preferred examples of the anode electrolyte 116 used in the anode electrolyte tank 115 of the present embodiment include water and an aqueous solution of sulfuric acid when a cation exchange membrane is used as the electrolyte membrane described later.
  • a cation exchange membrane is used as the electrolyte membrane described later.
  • water, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution can be mentioned.
  • Examples of the electrolyte membrane 102 in the method for producing ammonia of the present embodiment include polymer electrolyte membranes and reinforcing membranes.
  • a bipolar membrane and a mosaic charged membrane can be mentioned as composite charged membranes having a structure of a cation exchange membrane and an anion exchange membrane in one membrane.
  • electrolyte membranes include Nafion membrane (registered trademark) from DuPont, Aquivion membrane (registered trademark) from Solvay, Flemion membrane (registered trademark) from AGC, Aciplex (registered trademark) from Asahi Kasei, Dow Dow membrane (registered trademark) of the company, sulfonated polyether ketone polymer membrane, sulfonated polyether sulfone polymer membrane, sulfonated polyether ether sulfone polymer membrane, sulfonated polysulfide polymer membrane, sulfonated polyphenylene polymer membrane, poly as reinforcement Gore select membrane (registered trademark) of Gore Japan LLC impregnated with perfluorosulfonic acid polymer using tetrafluoroethylene (PTFE) porous material, membrane reinforced with PTFE woven fabric, polyethylene (PE) porous material and polypropylene ( PP) Membrane
  • PTFE te
  • Nafion membrane registered trademark
  • Aquivion membrane registered trademark
  • Gore Select membrane from Gore Japan LLC.
  • FAP-450 membrane of Fumasep membrane (registered trademark) of FuMA-Tech, FAA-3 membrane, ASVN membrane of Selemion membrane (registered trademark) of AGC, and AHO films are preferred.
  • the electrolyte membrane 102 in the ammonia production method of the present embodiment is more preferably Nafion membrane (registered trademark) and Aquivion membrane (registered trademark) of cation exchange membranes.
  • the reaction temperature in the ammonia production method of the present embodiment is not limited as long as the reaction proceeds, but is preferably -40°C to 120°C, more preferably -20°C to 80°C, and -5°C to 50°C. Even more preferred.
  • the reaction atmosphere in the ammonia production method of the present embodiment is usually carried out in a normal pressure atmosphere, but it can also be carried out in a pressurized atmosphere, and the outline is the ammonia production method and production apparatus described later.
  • the electrolytic device will be explained.
  • the reaction time in the method for producing ammonia of the present embodiment is not particularly limited, but usually it may be set in the range of several tens of minutes to several tens of hours, and it is possible to carry out the reaction continuously. It is also possible to stop the reaction in the middle. For example, after performing the reaction for several hours, it is possible to temporarily stop the reaction and then perform the reaction again.
  • FIG. 1 shows an ammonia electrolyzer (Part 1) 100 of Example 1 for producing ammonia
  • FIG. 2 shows an ammonia electrolyzer (Part 2) 200 of Example 2 for producing ammonia
  • FIG. 3 shows an ammonia electrolysis apparatus (part 3) 300 of Example 3 for producing ammonia
  • FIG. 4 shows an ammonia electrolysis apparatus (part 4) 400 of Example 4 for producing ammonia, respectively.
  • An ammonia electrolysis apparatus (part 1) 100 of the present embodiment includes a cathode 108 and an anode 118, and a membrane electrode assembly 131 in which a cathode catalyst layer 103 and an anode catalyst layer 113 are integrated via an electrolyte membrane 102.
  • Ammonia production equipment A cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and a cathode current collector 104 is arranged on the outside thereof, and an anode catalyst layer 113 is bonded to the other side of the electrolyte membrane 102, and the outside thereof.
  • the anode current collector 114 is arranged in the .
  • the cathode catalyst layer 103 comprises a catalyst body, and the anode catalyst layer 113 comprises an anode solid catalyst.
  • the manufacturing apparatus includes a cathode electrolyte bath 105 for a catholyte electrolyte 106 in liquid contact with a cathode 108 of a membrane electrode assembly 131, and an anode electrolyte for an anode electrolyte 116 in liquid contact with an anode 118 of a membrane electrode assembly 131.
  • a power source for supplying electrons to the cathode 108
  • an ion source for supplying ions to the cathode 108
  • the source of ions is electrolyte membrane 102 , catholyte 106 , anolyte 116 , both electrolyte membrane 102 and catholyte 106 , or both electrolyte membrane 102 and anolyte 116 .
  • it is an ammonia production apparatus for producing ammonia from nitrogen molecules by electrolysis.
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from a nitrogen cylinder 122 through a pipe 121 via a nitrogen cylinder regulator 123 and a nitrogen gas mass flow controller 124 .
  • Ammonia generated at the cathode 108 can be collected in the cathode electrolyte bath 105 of the cathode electrolyte 106 and the diluted sulfuric acid aqueous solution bath 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through a pipe 121 , a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126 .
  • the ammonia electrolysis apparatus (part 2) 200 of the present embodiment is an ammonia production apparatus including a cathode 108 composed of a cathode catalyst layer 103 and a cathode current collector 104 and a metal plate electrode 117 as an anode.
  • the cathode catalyst layer 103 comprises a catalyst body and is a gas diffusion electrode 133 .
  • the manufacturing apparatus includes an anode electrolyte bath 115 for an anode electrolyte 116 in liquid contact with the cathode catalyst layer 103, a power supply (power supply device 101) that supplies electrons to the cathode 108, and an ion source that supplies ions to the cathode 108. and means for supplying nitrogen gas to the cathode 108 .
  • the gas diffusion layer of the cathode catalyst layer 103 is preferably carbon paper made of polytetrafluoroethylene (hereinafter also referred to as "PTFE") and water-repellent-treated with a fluororesin for the cathode catalyst layer 103.
  • PTFE polytetrafluoroethylene
  • TGP-H-060H, TGP-H-090H, TGP-H-120H, EC-TP1-030T, EC-TP1-060T, EC-TP1-090T or EC-TP1-120T are preferred.
  • the source of ions is the anolyte 116 .
  • it is an ammonia production apparatus for producing ammonia from nitrogen molecules by electrolysis.
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from a nitrogen cylinder 122 through a pipe 121 via a nitrogen cylinder regulator 123 and a nitrogen gas mass flow controller 124 .
  • Ammonia produced at the cathode 108 can be collected in the anode electrolyte tank 115 of the anode electrolyte 116 and the diluted sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through a pipe 121 , a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126 .
  • the ammonia electrolysis apparatus (3) 300 of the present embodiment includes a cathode 108 and an anode 118, and a membrane electrode assembly 131 in which the cathode catalyst layer 103 and the anode catalyst layer 113 are integrated via the electrolyte membrane 102.
  • Ammonia production equipment A cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and a cathode current collector 104 is arranged on the outside thereof, and an anode catalyst layer 113 is bonded to the other side of the electrolyte membrane 102, and the outside thereof.
  • the anode current collector 114 is arranged in the .
  • the cathode catalyst layer 103 comprises a catalyst body, and the anode catalyst layer 113 comprises an anode solid catalyst.
  • the manufacturing apparatus includes an anode electrolyte bath 115 of an anode electrolyte 116 in liquid contact with an anode 118 of a membrane electrode assembly 131, a power supply (power supply device 101) for supplying electrons to the cathode 108, and ions for supplying ions to the cathode 108.
  • a supply ion source and means for supplying nitrogen gas to the catholyte 106 and the cathode 108 are provided.
  • the source of ions may be electrolyte membrane 102 , anolyte 116 , or both electrolyte membrane 102 and anolyte 116 . Furthermore, it is an ammonia production apparatus for producing ammonia from nitrogen molecules by electrolysis.
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from a nitrogen cylinder 122 through a pipe 121 via a nitrogen cylinder regulator 123 and a nitrogen gas mass flow controller 124 .
  • Ammonia generated at the cathode 108 can be collected in a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through a pipe 121 , a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126 .
  • the ammonia electrolysis apparatus (part 4) 400 of the present embodiment includes a cathode 108 comprising a cathode membrane electrode assembly 132 in which a cathode catalyst layer 103 is joined to one side of an electrolyte membrane 102, and a cathode current collector 104, and This is an ammonia production apparatus having a metal plate electrode 117 as an anode.
  • the cathode catalyst layer 103 has a catalyst body.
  • the manufacturing apparatus includes an anode electrolyte bath 115 of an anode electrolyte 116 in liquid contact with the electrolyte membrane 102 of the cathode membrane electrode assembly 132, a power supply (power supply device 101) for supplying electrons to the cathode 108, and An ion source for supplying ions and means for supplying nitrogen gas to the cathode 108 are provided.
  • the ion source is the electrolyte membrane 102 , the anolyte 116 , or both the electrolyte membrane 102 and the anolyte 116 .
  • it is an ammonia production apparatus for producing ammonia from nitrogen molecules by electrolysis.
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from a nitrogen cylinder 122 through a pipe 121 via a nitrogen cylinder regulator 123 and a nitrogen gas mass flow controller 124 .
  • Ammonia generated at the cathode 108 can be collected in a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • the by-produced hydrogen and unreacted nitrogen pass through a pipe 121, a diluted sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126.
  • the cathode current collector 104 and the anode current collector 114 in the electrolytic device of the present embodiment are, for example, carbon, metal, oxide, an alloy containing two or more kinds of metals, an oxide containing two or more kinds of metals, Examples include stainless steel, indium tin oxide, and indium zinc oxide.
  • metals include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, and gold.
  • oxides include titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, and silver oxide. , tantalum oxide, tungsten oxide, osmium oxide, iridium oxide, indium oxide, platinum oxide, and gold oxide.
  • the shape of the current collector in the electrolysis device of the present embodiment is not particularly limited as long as it is a shape through which the gas or the electrolytic solution can pass. Examples include cloth, nonwoven fabric, expanded material, porous material, and foamed material. In order to prevent corrosion during manufacturing by electrolysis, it is possible to use a current collector plated with gold or the like.
  • Nitrogen gas can be supplied from the nitrogen cylinder 122 by controlling the flow rate using the nitrogen cylinder regulator 123 and the nitrogen gas mass flow controller 124 .
  • a method of bubbling nitrogen gas into the electrolyte in the cathode electrolyte bath 105 in FIG. 1 and the electrolyte in the anode electrolyte bath 115 in FIG. 2 is also possible. It is also possible to supply nitrogen gas directly to the cathode catalyst layer 103 through the holes in the conductor 104 .
  • the electrolytic reaction for producing ammonia in the cathode catalyst layer 103 in the electrolytic device of this embodiment will be described.
  • a reaction occurs in which ammonia is produced from three of the electrons supplied from the power supply device 101, the nitrogen gas supplied to the cathode 108, and the ions supplied to the cathode 108.
  • the reaction formula is “N 2 +6e ⁇ +6H + ⁇ 2NH 3 ” when the above ions are protons, and “N 2 +6e ⁇ +6H 3 O + ⁇ 2NH 3 +6H 2 O”, and in the case of hydroxide ions, it can be formally described as “N 2 +6e ⁇ +6H 2 O ⁇ 2NH 3 +6OH ⁇ ”.
  • This by-produced hydrogen can take the form of being dissociated on the catalyst body, cathode solid catalyst, or catalyst support. and that adsorbed hydrogen dissociates into protons and hydrides on zinc oxide, which is a metal oxide. Therefore, in the method for producing ammonia of the present embodiment, at least one selected from the group consisting of activated hydrogen atoms, protons, and hydrides in the catalyst body, cathode solid catalyst, or catalyst support reacts to produce ammonia. It is speculated that it is a chemical species that promotes
  • Ammonia produced at the cathode 108 can be sent to the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia together with by-produced hydrogen and unreacted nitrogen. It is also possible to collect in the electrolytic solution used.
  • the electrolyte used in the cathode electrolyte bath 105 is preferably water or an aqueous solution of dilute sulfuric acid from the viewpoint of recovery and reuse. It is possible to raise it.
  • the mixed gas composed of ammonia produced in the cathode catalyst layer 103, by-produced hydrogen, and unreacted nitrogen in the electrolysis apparatus of the present embodiment is selected from ammonia by using water or a diluted sulfuric acid aqueous solution. Since the mixed gas of by-produced hydrogen and nitrogen can be taken out at the same time, hydrogen, which is useful as an energy carrier, can also be obtained in this embodiment. For safety, by-produced hydrogen can also be discharged to the outside through the draft device 126 .
  • the electrolytic reaction in the anode catalyst layer 113 or the metal plate electrode 117 in the electrolytic device of this embodiment will be described.
  • Oxygen, electrons and protons are generated from water or hydroxide ions by the catalyst of the anode 118.
  • the reaction formula is "2H 2 O ⁇ O 2 +4e ⁇ +4H + " or "4OH ⁇ ⁇ O 2 +2e ⁇ +2H 2 O”.
  • the produced protons or water pass through the electrolyte membrane 102 or the electrolytic solution and move to the cathode 108 , and the electrons pass through the anode current collector 114 or the metal plate electrode 117 and move to the power supply device 101 .
  • the generated oxygen can be partially dissolved in the water in the anode electrolyte bath 115 and released to the atmosphere.
  • the anode catalyst layer 113 (shown in FIGS. 1, 3 and 7) in the electrolytic device of this embodiment is selected from the group consisting of an anode solid catalyst, a catalyst carrier, a reaction field forming material, an electron conductor, an electrolyte and a gas diffusion layer. At least one selected.
  • the anode catalyst layer 113 is sometimes referred to as a gas diffusion electrode 133.
  • the solid catalyst in the anode catalyst layer 113 of the electrolytic device of this embodiment includes the same ones as those described in the solid catalyst and cathode solid catalyst in the method for producing ammonia of this embodiment.
  • a solid catalyst used on the anode side is defined as an anode solid catalyst, and preferred anode solid catalysts are iridium oxide catalyst, platinum catalyst, gold catalyst, silver catalyst, ruthenium catalyst, iridium catalyst, rhodium catalyst, palladium catalyst, osmium catalyst, and tungsten.
  • metals such as catalysts, lead catalysts, iron catalysts, chromium catalysts, cobalt catalysts, nickel catalysts, manganese catalysts, vanadium catalysts, molybdenum catalysts, gallium catalysts, aluminum catalysts, and alloys thereof; more preferred anode solid catalysts are Iridium oxide catalysts and platinum catalysts are included.
  • the catalyst carrier in the anode catalyst layer 113 of the present embodiment may conduct electrons, and is not particularly limited as long as it supports the catalyst of the present embodiment.
  • Examples of the catalyst carrier include the same ones as those described for the catalyst carrier in the cathode catalyst layer 103 in the method for producing ammonia of the present embodiment.
  • Preferred catalyst carriers in the anode catalyst layer 113 of the present embodiment include carbon black, for example, channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC and the like.
  • materials include activated carbon obtained by carbonizing and activating materials containing various carbon atoms, coke, natural graphite, artificial graphite, graphitized carbon, and the like.
  • Metal meshes include metal meshes such as nickel or titanium.
  • metal foams include metal foams such as aluminum, magnesium, titanium, zinc, iron, tin, lead, and alloys containing these.
  • metal oxides include aluminum oxide, oxide Zirconium, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, silver oxide, tantalum oxide, tungsten oxide , osmium oxide, iridium oxide, indium oxide, platinum oxide, gold oxide, magnesium oxide, silica, and the like.
  • composite oxides include silica-alumina, silica-magnesia, and the like.
  • carbon black, Ketjenblack, Ketjenblack EC, nickel metal mesh, titanium metal mesh and metal foam are more preferable in terms of high specific surface area and excellent electronic conductivity, and more durable. Titanium metal mesh and metal foam are even more preferred due to their superior properties.
  • the electron conductor in the anode catalyst layer 113 of the present embodiment is not particularly limited as long as it conducts electrons, and may serve as a catalyst carrier.
  • the same materials as those described for the electron conductor in the catalyst layer 103 can be used.
  • the electronic conductor of the present embodiment carbon black, Ketjenblack, Ketjenblack EC, nickel metal mesh, titanium metal mesh and metal foam are used because of their high specific surface area and excellent electronic conductivity.
  • IFPC40 and IFPC40-II manufactured by Ishifuku Metal Industry Co., Ltd., TEC10E40E, TEC10E50E, TEC10E60TPM, TEC10E70TPM, TEC10V30E, TEC10V40E, TEC10V50E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., Johnson Matthey Fuels. ⁇ HiSPEC4000 manufactured by Japan Co., Ltd., etc. can be mentioned.
  • the electrolyte in the anode catalyst layer 113 of this embodiment is not particularly limited as long as it is responsible for ion conduction.
  • the same as those described in the electrolyte in the cathode catalyst layer 103 of the present embodiment can be used.
  • the electrolyte in the anode catalyst layer 113 of the present embodiment when a cation exchange membrane is used as the electrolyte membrane described later, one that conducts at least one of protons and hydroxonium ions is preferable. trademark) and Aquivion® are preferred.
  • an anion exchange membrane is used as the electrolyte membrane to be described later, it is preferable to conduct hydroxide ions, and FAA-3-SOLUT-10 and AS-4 are preferable.
  • the gas diffusion layer in the anode catalyst layer 113 of this embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and electrolyte diffusion.
  • the same materials as those described in the gas diffusion layer in the cathode catalyst layer 103 of the present embodiment can be mentioned, and carbon paper is preferable.
  • Specific examples include TGP-H-060 and TGP-H- 090, TGP-H-120, TGP-H-060H, TGP-H-090H, TGP-H-120H, Electrochem EC-TP1-030T, EC-TP1-060T, EC-TP1-090T, EC- TP1-120T, SIGRACET 22BB, 28BC, 36BB, 39BB and the like.
  • TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H and EC-TP1-060T are preferable for the gas diffusion layer.
  • the metal of the metal plate electrode 117 of the present embodiment include stainless steel, indium tin oxide, indium zinc oxide, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, Niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, gold metals and alloys thereof.
  • platinum is preferred.
  • the shape of the metal plate electrode 117 includes, for example, a linear shape, a bar shape, a plate shape, a foil shape, a mesh shape, a woven fabric, a nonwoven fabric, an expanded body, a porous body, a foamed body, and the like, and preferably a mesh shape and a porous body. body.
  • FIG. 5 shows a chart of IR measurement of the sintered body (a1).
  • FIG. 6 shows a chart of IR measurement of Ketjenblack EC.
  • reaction vessel was cooled to room temperature of 20 to 25° C., ion-exchanged water (5 mL) and 2 mol/L sulfuric acid (10 mL) were added in this order to the reactor, and the mixture was stirred for 1 hour. Next, this reaction mixture was filtered through a vacuum filter equipped with silica filter paper, and then washed with 2 mol/L sulfuric acid (5 mL). Next, it was washed with ion-exchanged water until the hydrogen ion exponent (pH) of the filtrate became neutral. After adding this crude product to an eggplant flask, it is installed in an evaporator connected to a vacuum pump and dried at a bath temperature of 90 ° C. until it becomes a constant weight, and the rare earth metal-carbon-based composite (b3) is converted into a black color. Obtained as a solid (0.78 g).
  • the crucible was placed in a tabletop high-speed heating electric furnace MSFT-1520-P-TR (manufactured by Yamada Denki Co., Ltd.), heated at a rate of 10° C. per minute, and fired at a firing temperature of 400° C. for 2 hours. After the firing, a black fired product (0.80 g, 61% recovery when the charged weight was 100%) was obtained.
  • MSFT-1520-P-TR manufactured by Yamada Denki Co., Ltd.
  • sodium hydroxide aqueous solution (1 mol / L) is added to the reaction vessel so that the hydrogen ion exponent (pH) of the aqueous dispersion is 7, and stirred at room temperature 20 to 25 ° C. for 24 hours. did.
  • the content in the aqueous dispersion was separated by filtration by suction filtration, washed with water, and dried for 12 hours in a dryer (manufactured by Yamato Scientific Co., Ltd., DV400) set at a drying temperature of 373 K.
  • the average particle size of the obtained alumina-supported gold catalyst (SC1) was 10.1 nm by TEM analysis (the transmission electron microscope was JEM-2200FS manufactured by JEOL Ltd.), and powder XRD analysis (X-ray As a diffractometer, LabX XRD-6100 manufactured by Shimadzu Corporation was used.), the wavelength was 9.0 nm, and 5% by weight of gold was supported on alumina.
  • reaction mixture (part 1) is distilled off, and tetrahydrofuran (1 mL, manufactured by Kanto Kagaku Co., Ltd.) is added to give a reaction mixture (part 2) (PNP ligand represented by formula (d4)
  • a derivative concentration 0.024 mol/L in tetrahydrofuran solution
  • 5 wt % gold/total amount, weight ratio
  • SC1 alumina-supported gold catalyst (195.8 mg, 0.05 mmol of gold catalyst, 0.008 mmol of gold catalyst on alumina surface) was added to the reaction vessel.
  • Quantitative analysis of the resulting PNP ligand derivative (d5) was performed using an elemental analyzer (J Science Lab Co., JM10) for carbon, hydrogen, and nitrogen, and using an inductively coupled plasma for phosphorus, sulfur, and gold. It was carried out using an emission spectrometer (ICP-OES 5110 manufactured by Agilent). The quantitative analysis results are described below in weight percent. Hydrogen: 0.58 wt%, Carbon: 0.68 wt%, Nitrogen: Undetected Phosphorus: 0.08 wt%, Sulfur: 0.03 wt%, Gold: 3.0 wt%
  • Quantitative analysis of the obtained catalyst (dA1) was performed by the same method as described above for carbon, hydrogen, nitrogen, phosphorus, sulfur and gold, and by a sample combustion apparatus and ion chromatography (manufactured by Mitsubishi Analytic Tech, AQF-2100H) for iodine. and Thermo, ICS-1600), and molybdenum was measured using an inductively coupled plasma emission spectrometer (Agilent, ICP-OES 5110). The quantitative analysis results are described below in weight percent.
  • a cathode catalyst layer 103 which is a catalyst body for producing ammonia, was produced as follows.
  • the catalyst ink A used for the cathode 108 is an ink for applying the cathode solid catalyst of the present embodiment to the cathode catalyst layer 103 .
  • Carbon black-supported platinum catalyst as a solid catalyst (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 46.6% by weight, product name "TEC10E50E”), rare earth metal-carbon-based bond (b1), 2-propanol (Fujifilm Sum Catalyst Ink A was prepared using a Nafion Dispersion Solution (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., product name "5% Nafion Dispersion Solution DE520 CS Type”) as an electrolyte.
  • a Nafion Dispersion Solution manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., product name "5% Nafion Dispersion Solution DE520 CS Type
  • Carbon-supported platinum catalyst, rare earth metal-carbon-based composite (b1), Nafion dispersion solution and 2-propanol are added in this order to a glass vial bottle, and the resulting dispersion solution is Catalyst ink A was prepared by irradiating ultrasonic waves for 30 minutes with the oscillation power set to "High" using a sonic washer ASU-6.
  • the ratio of Nafion (hereinafter also referred to as "ionomer”) in the above catalyst ink will be explained.
  • the ionomer ratio (% by weight) calculated from the following formula was adjusted to 31% by weight.
  • Proportion of ionomer (% by weight) [Ionomer solid content (weight) / [ ⁇ carbon-supported platinum catalyst (weight) + ionomer solid content (weight) + rare earth metal-carbon-based composite (weight) ⁇ ]] ⁇ 100
  • this catalyst ink A is applied to fixed carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) at a room temperature of 20 to 25° C., and is applied on a hot plate set to 80° C. Water and alcohols, which are solvent components in the catalyst ink, were dried. The coating amount was adjusted so that the amount of platinum per 1 cm 2 was 1.0 mg.
  • GDE gas diffusion electrode 133
  • the gas diffusion electrode 133 is a 2.7 ⁇ 2 electrode coated with a platinum catalyst (7.3 mg), which is a solid catalyst, and a rare earth metal-carbon-based composite (b1) (12.0 mg).
  • the gas diffusion electrode 133 was a square of 0.7 cm 2 and was designated "GDE-Cathode-1a".
  • a catalyst ink B was prepared by applying the complex of the present embodiment to the cathode catalyst layer 103 .
  • Catalyst body represented by formula (dA1) (Of 6.0 mg, the number of moles per molybdenum is 0.144 ⁇ mol by inductively coupled plasma emission spectroscopy)) is dissolved in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (1.0 mL). The resulting solution was used as catalyst ink B.
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, is composed of a platinum catalyst (7.3 mg) which is a solid catalyst, a rare earth metal-carbon-based bond (b1) (12.0 mg), and formula (dA1 ) (0.12 mg, 0.0029 ⁇ mol per molybdenum) coated with a gas diffusion electrode 133, which is a square of 2.7 ⁇ 2.7 cm 2 , and is referred to as “GDE-Cathode- 1”.
  • the anode catalyst layer 113 was produced as follows. This ink is used to apply the anode solid catalyst of the present embodiment to the anode catalyst layer 113 .
  • Carbon black-supported platinum catalyst manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 46.6% by weight, product name "TEC10E50E" as a solid catalyst, 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and Nafion dispersion as an electrolyte
  • a catalyst ink C was prepared using a solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., product name “5% Nafion dispersion solution DE520 CS type”).
  • Carbon-supported platinum catalyst, Nafion dispersion solution and 2-propanol are added in this order to a glass vial bottle, and the resulting dispersion solution is oscillated using an ultrasonic cleaner ASU-6 manufactured by AS ONE.
  • Catalyst ink C was prepared by setting the power to "High” and irradiating ultrasonic waves for 30 minutes. Next, this catalyst ink C was applied to fixed carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) at a room temperature of 20 to 25° C., and on a hot plate set to 80° C., Water and alcohols, which are solvent components in the catalyst ink, were dried.
  • the coating amount was adjusted so that the amount of platinum per 1 cm 2 was 1.0 mg.
  • a gas diffusion electrode 133 containing Nafion as an electrolyte and carbon-supported platinum catalyst as a solid catalyst was produced.
  • the gas diffusion electrode 133 is a square gas diffusion electrode 133 of 2.7 ⁇ 2.7 cm 2 coated with a platinum catalyst (7.3 mg), which is a solid catalyst. GDE-1".
  • the proportion of ionomer in the above catalyst ink will be explained.
  • the ionomer ratio (% by weight) calculated from the following formula was adjusted to 26% by weight.
  • a membrane electrode assembly (hereinafter also referred to as "MEA") consisting of the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • MEA membrane electrode assembly
  • Nafion 212 membrane registered trademark manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm x 4 cm) was used.
  • the "GDE-Cathode-1" of the gas diffusion electrode 133 which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane, and the "GDE-1" of the gas diffusion electrode 133, which is the anode catalyst layer, is arranged on the other side of the ion exchange membrane.
  • the membrane electrode assembly "MEA-1" was produced by thermocompression bonding under the conditions of a temperature of 132° C., a load of 5.4 kN, and a bonding time of 240 seconds.
  • a stainless steel current collector having 25 circular holes with a diameter of 2.5 mm was provided together with a Teflon (registered trademark) sheet frame as a gasket for electrolysis. It was attached to the liquid bath, and the electrolytic device (part 1) 100 described in FIG. 1 was assembled.
  • a cathode membrane electrode assembly 132 consisting of the electrolyte membrane 102 and the cathode catalyst layer 103 was produced as follows.
  • the ion exchange membrane used for the electrolyte membrane Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm x 4 cm) was used.
  • the "GDE-Cathode-1" of the gas diffusion electrode 133 is placed on one side of the ion exchange membrane, and the cathode membrane is bonded by thermocompression under the conditions of a temperature of 132° C., a load of 5.4 kN, and a bonding time of 240 seconds.
  • a stainless steel collector having 25 circular holes with a diameter of 2.5 mm was attached to the side of "MEA-2" which was not on the side of the electrolyte membrane.
  • a platinum mesh electrode was used as the metal plate electrode 117 for the anode.
  • An ammonia electrolysis apparatus (part 4) 400 shown in FIG. 4 and equipped with the two electrodes was assembled.
  • Ammonia was produced by electrolysis under the following conditions using the electrolytic apparatus (Part 1) assembled as described above for producing ammonia.
  • Device body temperature 25-28°C (room temperature)
  • Power supply 101 Versa STAT4 from Princeton Applied Research was used to measure voltage and current.
  • Cathode electrolyte bath 105 0.02 mol/L sulfuric acid aqueous solution (6 mL)
  • Anode electrolyte tank 115 0.02 mol/L sulfuric acid aqueous solution (6 mL)
  • Measurement conditions Constant potential measurement was performed at -2.3V.
  • Ammonia was quantified using a Thermo Scientific Dionex ion chromatography (IC) system, Dionex Integrion from Thermo.
  • the amount of ammonia in the aqueous sulfuric acid solution in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia and in the aqueous sulfuric acid solution in the cathode electrolytic solution tank 105 was quantified to obtain the amount of generated ammonia.
  • the amount of ammonia produced per complex in the catalyst was defined as the catalyst turnover number, which was calculated by the following formula.
  • the conversion efficiency was calculated from the amount of electricity used in the Versa STAT4 data of the power supply 101 .
  • Catalyst turnover speed (mol/mol) [ammonia production amount ( ⁇ mol)/moles of molybdenum in catalyst body ( ⁇ mol)] (mol/mol)
  • Test Example 2 Electrolysis of ammonia in the same manner as in Test Example 1 described above, except that the following "GDE-Cathode-2" is used for the cathode catalyst layer 103 instead of "GDE-Cathode-1" used in Test Example 1.
  • An apparatus (part 1) 100 was produced, and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1.
  • "GDE-Cathode-2” will be described in detail.
  • Test Example 1 described above except that the rare earth metal-carbon-based composite (b1) used in Test Example 1 was changed to the fired body (c3), and the amount used was changed from 76.1 mg to 53.8 mg.
  • 'GDE-Cathode-2a' was prepared in the same manner as above.
  • the amount of catalyst ink B applied was changed from 20 ⁇ L in Test Example 1 to 10 ⁇ L, and the catalyst ink B was applied to the gas diffusion electrode 133 “GDE-Cathode-3” to prepare the cathode catalyst layer 103 .
  • the gas diffusion electrode 133 includes a platinum catalyst (7.3 mg) which is a solid catalyst, a sintered body (c3) (8.5 mg), and a catalyst body (0.06 mg) represented by the formula (dA1).
  • a platinum catalyst 7.3 mg
  • c3 sintered body
  • 0.0014 ⁇ mol per molybdenum was applied to the gas diffusion electrode 133, which was a square of 2.7 ⁇ 2.7 cm 2 and was designated as “GDE-Cathode-2”.
  • the gas diffusion electrode 133 with the anode catalyst layer 113 was the same "GDE-1" as in Test Example 1. The results of this test example are shown in Table 2 below.
  • Test Example 3 Electrolysis of ammonia in the same manner as in Test Example 1 described above, except that the following "GDE-Cathode-3" is used in place of "GDE-Cathode-1" used in Test Example 1 for the cathode catalyst layer 103.
  • An apparatus (part 1) 100 was produced, and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1. "GDE-Cathode-3" will be specifically described.
  • An ammonia electrolytic device (part 1) was produced in the same manner as in Test Example 1 above, except that the rare earth metal-carbon-based composite (b1) used in Test Example 1 was not used, and the same procedure was performed as in Test Example 1. was produced by the electrolysis of ammonia.
  • Cathode catalyst layer 103 was prepared by applying catalyst ink B (20 ⁇ L) to “GDE-1” of gas diffusion electrode 133 .
  • the gas diffusion electrode 133 is coated with a platinum catalyst (7.3 mg), which is a solid catalyst, and a catalyst represented by formula (dA1) (0.12 mg, 0.0029 ⁇ mol per molybdenum).
  • the gas diffusion electrode 133 which is a square of 2.7 ⁇ 2.7 cm 2 , was designated as “GDE-Cathode-3”.
  • the gas diffusion electrode 133 with the anode catalyst layer 113 was the same "GDE-1" as in Test Example 1. The results of this test example are shown in Table 3 below.
  • Test Example 4 Electrolysis of ammonia in the same manner as in Test Example 1 described above, except that the following "GDE-Cathode-4" is used in the cathode catalyst layer 103 instead of "GDE-Cathode-1" used in Test Example 1.
  • An apparatus (part 1) 100 was produced, and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1. "GDE-Cathode-4" will be specifically described.
  • An ammonia electrolysis device (part 1) was produced in the same manner as in Test Example 1 described above, except that the platinum catalyst and the rare earth metal-carbon-based composite (b1), which are the solid catalysts used in Test Example 1, were not used. , production by electrolysis of ammonia was carried out in the same manner as in Test Example 1.
  • Cathode catalyst layer 103 was prepared by coating carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) with catalyst ink B (20 ⁇ L) alone.
  • the gas diffusion electrode 133 is a 2.7 ⁇ 2.7 cm 2 square coated with a catalyst represented by formula (dA1) (0.12 mg, 0.0029 ⁇ mol per molybdenum).
  • a gas diffusion electrode 133 designated "GDE-Cathode-4".
  • the gas diffusion electrode 133 with the anode catalyst layer 113 was the same "GDE-1" as in Test Example 1. The results of this test example are shown in Table 4 below.
  • Test Example 5 Electrolysis of ammonia in the same manner as in Test Example 1 described above, except that the following "GDE-Cathode-5" is used in place of "GDE-Cathode-1" used in Test Example 1 for the cathode catalyst layer 103.
  • An apparatus (part 1) 100 was produced, and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1.
  • "GDE-Cathode-5" will be specifically described. Except for using the thiol compound represented by the formula (T1) without using the platinum catalyst and the rare earth metal-carbon-based conjugate (b1) which are the solid catalysts used in Test Example 1, Test Example 1 described above.
  • An ammonia electrolysis device (part 1) was produced in the same manner as in , and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1.
  • ⁇ Preparation conditions for catalyst ink D> A catalyst ink D was prepared by applying the complex of the present embodiment to the cathode catalyst layer 103 .
  • Compounds represented by formula (T1) and formula (O1) were mixed in tetrahydrofuran and reacted to prepare a catalyst ink D.
  • the hydroxyl group of the compound represented by the formula (O1) reacts with the compound represented by the formula (T1), and may pass through the onium compound represented by the formula (FO2a) or the like.
  • a polymer having a siloxane bond represented by the formula (TE1) is formed in the cathode catalyst layer 103, and further, the thiol group of the polymer is formed between the metal atom on the surface of the metal catalyst and the metal thiol. Assuming that they will be combined, a catalyst ink was produced.
  • a thiol compound represented by the formula (T1) 100 mg, 0.55 mmol
  • an ionic liquid represented by the formula (O1) 448 mg, 1.10 mmol
  • tetrahydrofuran 200 ⁇ L
  • ultrasonic waves were applied for 30 minutes with the oscillation power set to "High” using an ultrasonic cleaner ASU-6 manufactured by AS ONE.
  • Catalyst ink D was prepared by dispersing this catalyst ink D1 (10 mg) in dichloromethane (50 mL). Catalyst ink B (20 ⁇ L) and catalyst ink D (50 ⁇ L) were applied to carbon paper (manufactured by Toray Industries, product name “TGP-H-060H”, square of 2.7 ⁇ 2.7 cm 2 ), A cathode catalyst layer 103 was produced.
  • the gas diffusion electrode 133 is composed of a catalyst represented by the formula (dA1) (0.12 mg, 0.0029 ⁇ mol per molybdenum) and a thiol compound represented by the formula (T1) (0.008 ⁇ mol).
  • gas diffusion electrode 133 which is a square of 2.7 ⁇ 2.7 cm 2 , and is designated as “GDE-Cathode-5”.
  • the gas diffusion electrode 133 with the anode catalyst layer 113 was the same "GDE-1" as in Test Example 1.
  • a catalyst body represented by the formula (d7-A1-N 2 ) is produced by thermocompression bonding to produce a membrane electrode assembly and conditioning the electrolytic device. However, we believe that it can be fabricated in the cathode catalyst layer. The results of this test example are shown in Table 5 below.
  • a platinum catalyst that is a solid catalyst was selected from a gold catalyst derived from a catalyst body represented by the formula (d7-A1-N 2 ) and a supported molecular catalyst. It was possible to confirm the same amount of ammonia production as in Test Example 3 using .
  • the site where the gold thiol bond on the surface of the gold catalyst is absent is subordinate in the cathode catalyst layer.
  • Generated hydrogen gas is evenly diverged and stored as active hydrogen, receives protons from the electrolyte membrane and electrolyte solution and electrons from the electrode and stores them as active hydrogen, and ammonia synthesis of the supported molybdenum complex is performed by the stored activity. It is presumed that there is a role to accelerate the reaction by utilizing hydrogen. In addition, when producing a catalyst body, the ratio of sites having gold thiol bonds and sites not having gold thiol bonds on the surface of the gold catalyst can be adjusted by adjusting the amount of the thiol compound used. It is speculated that by-product hydrogen can be suppressed at the sites that have them.
  • water repellency and gas permeability can be improved.
  • water repellency contributes to improved transport of water, protons, oxonium ions, ammonia, and ammonium ions in the cathode catalyst layer. It is speculated that it contributes to the efficient delivery of nitrogen gas.
  • an example in which the ionic liquid represented by the formula (O1) used for producing the cathode catalyst layer is supported in the vicinity of the gold catalyst is represented by the formula (d8-A1-N 2 ) catalytic body (a) to (c) of the structure represented by (X b- is the same as above).
  • (a) is the case where the ionic liquid is supported by covalent bonds
  • (b) is the case where the ionic liquid is supported by hydrogen bonds formed at the portion where the siloxane bond is interrupted
  • (c) is the case where water It is speculated that the ionic liquid is supported by hydrogen bonding through molecules, and it is thought that the reaction site for ammonia generation is provided by allowing the ionic liquid to stay at the active site of the reaction.
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, comprises a platinum catalyst (7.3 mg), which is a solid catalyst, and a catalyst represented by the formula (dA1) (0.12 mg, per molybdenum 0.0029 ⁇ mol) was applied to the gas diffusion electrode 133, which was a square of 2.7 ⁇ 2.7 cm 2 and designated as “GDE-Cathode-3”.
  • the gas diffusion electrode 133 with the anode catalyst layer 113 is specifically a gas diffusion electrode 133 coated with iridium oxide, and this is designated as "GDE-2". The results of this test example are shown in Table 6 below.
  • Test Example 7 Electrolysis of ammonia in the same manner as in Test Example 1 described above, except that the following "GDE-Cathode-7" is used for the cathode catalyst layer 103 instead of "GDE-Cathode-1" used in Test Example 1.
  • An apparatus (part 1) 100 was produced, and production by electrolysis of ammonia was carried out in the same manner as in Test Example 1.
  • "GDE-Cathode-7” will be specifically explained.
  • An ammonia electrolyzer in the same manner as in Test Example 1 described above, except that povidone-iodine, which is a complex of polyvinylpyrrolidone and iodine, was used instead of the rare earth metal-carbon-based conjugate (b1) used in Test Example 1. (No.
  • a catalyst ink E was prepared by applying the complex of the present embodiment to the cathode catalyst layer 103 .
  • Povidone-iodine which is a complex of polyvinylpyrrolidone and iodine, was prepared by adding iodine (3.81 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and polyvinylpyrrolidone (2.26 g, manufactured by Tokyo Kasei Co., Ltd., K30, weight average molecular weight 40,000) in a mortar.
  • Powder A as povidone-iodine was prepared by mixing and pulverizing (6.07 g). After adding this powder (0.16 g) and water (10 mL) to the vial, set the oscillation power to "High” using an ultrasonic cleaner ASU-6 manufactured by AS ONE at 30 to 40 ° C. A suspension was prepared by irradiating ultrasonic waves for 30 minutes, and this was used as catalyst ink E. The catalyst ink B (20 ⁇ L) and the catalyst ink E (10 ⁇ L) were applied to the “GDE-1” of the gas diffusion electrode 133 to prepare the cathode catalyst layer 103 .
  • the gas diffusion electrode 133 is coated with the catalyst represented by the formula (dA1) (0.12 mg, 0.0029 ⁇ mol per molybdenum) and the powder A (0.16 mg).
  • the gas diffusion electrode 133 is a square of 2.7 ⁇ 2.7 cm 2 and is designated as “GDE-Cathode-7”.
  • the gas diffusion electrode 133 with the anode catalyst layer 113 was the same "GDE-1" as in Test Example 1.
  • a membrane electrode assembly produced in the same manner as in Test Example 1 was designated as "MEA-7". The results of this test example are shown in Table 7 below.
  • Test Example 8 The membrane electrode assembly "MEA-7" produced in Test Example 7 was replaced with a JARI standard cell instead of the ammonia electrolysis device (Part 1) 100 described in Test Example 1, and some of the parts were changed. Then, an ammonia electrolysis apparatus (No. 5) 500 shown in FIG. 7 was assembled.
  • the JARI standard cell is a cell developed by the Japan Automobile Research Institute (JARI) for research and development of polymer electrolyte fuel cells. Among the parts used in the JARI standard cell, the changed parts are the carbon separator shown in FIG.
  • Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia 0.02 mol/L sulfuric acid aqueous solution (10 mL) Measurement conditions: Constant potential measurement was performed at -2.3V. The power supply was stopped every hour of the reaction time, and the cathode catalyst layer was rinsed with a 0.02 mol/L sulfuric acid aqueous solution (6 mL). The amount of ammonia in the aqueous sulfuric acid solution in the dilute sulfuric acid aqueous solution tank 125 for trapping ammonia and in the aqueous sulfuric acid solution used to rinse the cathode catalyst layer 103 was quantified to determine the amount of ammonia produced. The results of this example are shown in Table 8 below.
  • the present invention can be used for a method for producing ammonia.
  • Ammonia Electrolyzer (Part 1) 101 power supply device 102 electrolyte membrane 103 cathode catalyst layer (catalyst layer for producing ammonia) 104 cathode current collector 105 cathode electrolyte bath 106 cathode electrolyte 108 cathode (cathode catalyst layer and cathode current collector) 113 anode catalyst layer 114 anode current collector 115 anode electrolyte tank 116 anode electrolyte 117 metal plate electrode 118 anode (anode catalyst layer and anode current collector, or metal plate electrode) 121 Piping 122 Nitrogen cylinder 123 Nitrogen cylinder regulator 124 Nitrogen gas mass flow controller 125 Dilute sulfuric acid aqueous solution tank for collecting ammonia 126 Draft device 131 Membrane electrode assembly 132 Cathode membrane electrode assembly 133 Gas diffusion electrode (GDE) 141 Electrolysis cell 200 Ammonia electrolysis device (Part 2) 300 Ammonia Electrolyzer (Part 3) 400 Ammonia

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WO2024185808A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造装置
WO2024185807A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造方法
WO2024232396A1 (ja) * 2023-05-09 2024-11-14 有限会社ターナープロセス アンモニア系化合物の製造方法およびアンモニア系化合物の製造装置
CN116651512A (zh) * 2023-08-02 2023-08-29 北京理工大学 一种强可见光吸收的Ru-Fe环状光催化剂及其制备方法
CN116651512B (zh) * 2023-08-02 2023-10-24 北京理工大学 一种强可见光吸收的Ru-Fe环状光催化剂及其制备方法
WO2025183187A1 (ja) * 2024-03-01 2025-09-04 出光興産株式会社 含窒素化合物合成用還元剤
WO2025183223A1 (ja) * 2024-03-01 2025-09-04 出光興産株式会社 含窒素化合物合成用還元剤

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