US20160177459A1 - Electrochemical reduction device - Google Patents

Electrochemical reduction device Download PDF

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US20160177459A1
US20160177459A1 US15/054,610 US201615054610A US2016177459A1 US 20160177459 A1 US20160177459 A1 US 20160177459A1 US 201615054610 A US201615054610 A US 201615054610A US 2016177459 A1 US2016177459 A1 US 2016177459A1
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electrode
reduction
layer
reduction device
oxygen generating
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Yasushi Sato
Kota Miyoshi
Kojiro NAKAGAWA
Yoshihiro Kobori
Shinji Oshima
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Eneos Corp
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JX Nippon Oil and Energy Corp
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Assigned to JX NIPPON OIL & ENERGY CORPORATION reassignment JX NIPPON OIL & ENERGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOBORI, YOSHIHIRO, NAKAGAWA, Kojiro, MIYOSHI, KOTA, OSHIMA, SHINJI, SATO, YASUSHI
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    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/0405—
    • C25B11/0447—
    • C25B11/0484—
    • 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
    • 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
    • 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
    • C25B11/093—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 noble metal or noble metal oxide and at least one 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B9/08—
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a technique for electrochemically hydrogenating an aromatic compound.
  • a cyclic organic compound such as cyclohexane or decalin can be efficiently obtained by hydrogenating at least one benzene ring of a corresponding aromatic hydrocarbon compound (benzene or naphthalene) with the use of hydrogen gas.
  • This reaction requires reaction conditions of high temperature and high pressure, and hence it is not suitable for small and medium scale manufacturing of cyclic organic compounds.
  • an electrochemical reaction using an electrolysis cell proceeds without gaseous hydrogen being required and under relatively mild reaction conditions (from normal temperature to approximately 200° C. and normal pressure) because water can be used as a hydrogen source.
  • the present inventors have studied a method in which a liquid aromatic hydrocarbon compound is directly introduced into the reduction electrode side of an electrolysis cell.
  • This method has the advantage that an electrolytic hydride-producing reaction can be caused to proceed at a higher current density in comparison with a method in which a vaporized aromatic hydrocarbon compound is introduced.
  • a technique, for causing a hydride-producing reaction for an aromatic hydrocarbon compound supplied in a liquid state to proceed more efficiently, has not been studied sufficiently, and there remains a challenge to be addressed.
  • the present invention has been made in view of such a challenge, and a purpose of the invention is to provide a technique in which a hydride of an aromatic compound can be produced at a high efficiency by an electrochemical reaction.
  • An embodiment of the present invention is an electrochemical reduction device.
  • the electrochemical reduction device comprises: an electrolyte membrane having proton conductivity; a reduction electrode including a reduction electrode catalyst layer that is provided in contact with one major surface of the electrolyte membrane and has an electron conductive material and a metal containing one or both of Pt and Pd supported by the electron conductive material, a diffusion layer that is provided near to the other major surface of the reduction electrode catalyst layer, the other major surface being opposite to the electrolyte membrane, and that causes a liquid aromatic compound and a hydride of the aromatic compound to pass through, and a dense layer provided between the diffusion layer and the reduction electrode catalyst layer; an oxygen generating electrode provided in contact with the other major surface of the electrolyte membrane; a raw material supplier that supplies the aromatic compound in a liquid state to the reduction electrode; a moisture supplier that supplies water or humidified gas to the oxygen generating electrode; and a power controller that externally applies an electric field such that the reduction electrode has an electronegative potential and the oxygen generating electrode has an electro
  • FIG. 1 is a schematic view illustrating a schematic configuration of an electrochemical reduction device according to an embodiment
  • FIG. 2 is an exploded perspective view illustrating a schematic configuration of an electrode unit included in the electrochemical reduction device according to an embodiment
  • FIG. 3 is a side view illustrating a schematic configuration of an electrode unit included in the electrochemical reduction device according to an embodiment
  • FIG. 4 is a schematic view illustrating an enlarged example of a sectional structure of an oxygen generating electrode.
  • FIG. 5 is a graph showing I-V curves obtained by respective electrode units of Examples from 1 to 5 and Comparative Example 1.
  • An embodiment of the present invention is an electrochemical reduction device.
  • the electrochemical reduction device comprises: an electrolyte membrane having proton conductivity; a reduction electrode including a reduction electrode catalyst layer that is provided in contact with one major surface of the electrolyte membrane and has an electron conductive material and a metal containing one or both of Pt and Pd supported by the electron conductive material, a diffusion layer that is provided near to the other major surface of the reduction electrode catalyst layer, the other major surface being opposite to the electrolyte membrane, and that causes a liquid aromatic compound and a hydride of the aromatic compound to pass through, and a dense layer provided between the diffusion layer and the reduction electrode catalyst layer; an oxygen generating electrode provided in contact with the other major surface of the electrolyte membrane; a raw material supplier that supplies the aromatic compound in a liquid state to the reduction electrode; a moisture supplier that supplies water or humidified gas to the oxygen generating electrode; and a power controller that externally applies an electric field such that the reduction electrode has an electronegative potential and the oxygen generating electrode has an electro
  • the diffusion layer may have a fiber-like shape or a shape in which many particles are solidified.
  • the diffusion layer may contain a carbon fiber. Additionally, the diffusion layer may contain a material having electron conductivity of 1.0 ⁇ 10 ⁇ 2 S/cm or more.
  • the dense layer may contain a mixture of an electron conductive powder and a water repellent.
  • FIG. 1 is a schematic view illustrating a schematic configuration of an electrochemical reduction device 10 according to an embodiment.
  • FIG. 2 is an exploded perspective view illustrating a schematic configuration of an electrode unit included in the electrochemical reduction device 10 according to an embodiment.
  • FIG. 3 is a side view illustrating a schematic configuration of an electrode unit included in the electrochemical reduction device 10 according to an embodiment.
  • the electrochemical reduction device 10 includes an electrode unit 100 , a power controller 20 , an organic material storage tank 30 , a water storage tank 40 , a gas-water separation unit 50 , and a controller 60 .
  • the power controller 20 is, for example, a DC/DC converter for converting the output voltage of a power source into a predetermined voltage.
  • the positive electrode output terminal of the power controller 20 is connected to an oxygen generating electrode (positive electrode) 130 of the electrode unit 100 .
  • the negative electrode output terminal of the power controller 20 is connected to a reduction electrode (negative electrode) 120 of the electrode unit 100 .
  • a reference pole may be provided in the power controller 20 in order to detect the potentials of the positive and negative electrodes.
  • a reference pole input terminal is connected to a reference electrode 112 provided on the later-described electrolyte membrane 110 .
  • the outputs of the positive electrode output terminal and the negative electrode output terminal of the power controller 20 are controlled by the controller 60 such that the potentials of the oxygen generating electrode 130 and the reduction electrode 120 become desired ones based on the potential of the reference electrode 112 .
  • a power source is not particularly limited, and normal system power may be used, or electrical power derived from natural energy such as sunlight or wind power can also be used preferably.
  • the organic substance storage tank 30 stores an aromatic compound.
  • the aromatic compound used in the present embodiment is an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound, which contains at least one aromatic ring.
  • the aromatic compound include, for example, benzene, naphthalene, anthracene, diphenylethane, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, N-alkylpyrrole, N-alkylindole, N-alkyldibenzopyrrole, and the like. From one to four hydrogen atoms of an aromatic ring of anyone of the aforementioned aromatic hydrocarbon compounds or nitrogen-containing heterocyclic aromatic compounds may be substituted by alkyl groups.
  • alkyl of any one of the aromatic compounds is a C 1-6 straight or branched alkyl group.
  • alkylbenzenes include toluene, ethyl benzene, and the like
  • dialkylbenzenes include xylene, diethylbenzene, and the like
  • trialkylbenzenes include mesitylene and the like.
  • Alkylnaphthalenes include methylnaphthalene.
  • An aromatic ring of any one of the aromatic hydrocarbon compounds or nitrogen-containing heterocyclic aromatic compounds may have from 1 to 3 substituents.
  • the aromatic hydrocarbon compounds and the nitrogen-containing heterocyclic aromatic compounds may be collectively referred to as “aromatic compounds”.
  • the aromatic compound is a liquid at room temperature.
  • the mixture should be a liquid. Consequently, the aromatic compound can be supplied to the electrode unit 100 in a liquid state without being heated, pressurized, or the like, and hence the configuration of the electrochemical reduction device 10 can be simplified.
  • the concentration of the aromatic hydrocarbon compound in a liquid state is 0.1% or more, preferably 0.3% or more, and more preferably 0.5% or more.
  • the aromatic compound stored in the organic material storage tank 30 is supplied to the reduction electrode 120 of the electrode unit 100 by a first liquid supplier 32 .
  • a first liquid supplier 32 for example, various types of pumps such as a gear pump or a cylinder pump, or a gravity flow device or the like can be used.
  • an N-substitution product of the aforementioned aromatic compound may be used.
  • a circulation pathway is provided between the organic material storage tank 30 and the reduction electrode 120 of the electrode unit 100 .
  • the aromatic compound, a hydride of which has been produced by the electrode unit 100 , and an unreacted aromatic compound are stored in the organic material storage tank 30 after passing through the circulation pathway. No gas is generated by a major reaction that proceeds at the reduction electrode 120 of the electrode unit 100 , but if gas such as hydrogen is by-produced, a gas-liquid separation device may be provided in the middle of the circulation pathway.
  • the water storage tank 40 stores, for example, ion exchange water, pure water, an aqueous solution in which an acid such as sulfuric acid is added to ion exchange water or pure water, or the like (hereinafter, they are simply referred to as “water”).
  • the water stored in the water storage tank 40 is supplied to the oxygen generating electrode 130 of the electrode unit 100 by a second liquid supplier 42 .
  • the second liquid supplier 42 for example, various types of pumps such as a gear pump or a cylinder pump, or a gravity flow device or the like can be used, similarly to the first liquid supplier 32 .
  • a circulation pathway is provided between the water storage tank 40 and the oxygen generating electrode 130 of the electrode unit 100 .
  • the water that has not been reacted in the electrode unit 100 is stored in the water storage tank 40 after passing through the circulation pathway.
  • the gas-water separation unit 50 is provided in the middle of a pathway through which unreacted water is sent back to the water storage tank 40 from the electrode unit 100 . With the gas-water separation unit 50 , gas such as oxygen generated by the electrolysis of water in the electrode unit 100 is separated from water and discharged to the outside of the system.
  • the electrode unit 100 includes the electrolyte membrane 110 , the reduction electrode 120 having a reduction electrode catalyst layer 122 , a diffusion layer 140 , and a dense layer 142 , the oxygen generating electrode 130 , a separator 150 , and a current collector 160 .
  • the electrode unit 100 is illustrated in a simplified way in which the separator 150 and the current collector 160 are omitted.
  • the electrolyte membrane 110 is formed of a material (ionomer) having proton conductivity, and inhibits substances from getting mixed or being diffused between the reduction electrode 120 and the oxygen generating electrode 130 while selectively conducting protons.
  • the thickness of the electrolyte membrane 110 is preferably from 5 to 300 ⁇ m, more preferably from 10 to 150 ⁇ m, and most preferably from 20 to 100 ⁇ m. If the thickness of the electrolyte membrane 110 is less than 5 ⁇ m, the barrier property of the electrolyte membrane 110 is deteriorated, so that cross-leaking is likely to occur. On the other hand, if the thickness thereof is more than 300 ⁇ m, ion transfer resistance becomes too large, which is not preferred.
  • the area resistance of the electrolyte membrane 110 that is, the ion transfer resistance per geometric area thereof is preferably 2000 m ⁇ cm 2 or less, more preferably 1000 m ⁇ cm 2 or less, and most preferably 500 m ⁇ cm 2 or less. If the area resistance of the electrolyte membrane 110 is more than 2000 m ⁇ cm 2 , proton conductivity may become insufficient. Examples of the material having proton conductivity (i.e., a cation-exchanging ionomer) include perfluorosulfonic acid polymers such as NAFIONTM and FLEMIONTM.
  • the ion exchange capacity (IEC) of the cation exchange ionomer is preferably from 0.7 to 2 meq/g, and more preferably from 1 to 1.2 meq/g. If the ion exchange capacity thereof is less than 0.7 meq/g, ion conductivity may become insufficient. On the other hand, if the ion exchange capacity of the cation exchange ionomer is more than 2 meq/g, the solubility of the ionomer in water is increased, and hence the strength of the electrolyte membrane 110 may become insufficient.
  • the reference electrode 112 may be provided in an area spaced apart from the reduction electrode 120 and the oxygen generating electrode 130 so as to contact the electrolyte membrane 110 , as illustrated in FIG. 1 . That is, the reference electrode 112 is electrically isolated from the reduction electrode 120 and the oxygen generating electrode 130 .
  • the reference electrode 112 is held at a reference electrode potential V Ref .
  • V Ref a standard hydrogen reduction electrode
  • V Ref Ag/AgCl electrode
  • the current I flowing between the reduction electrode 120 and the oxygen generating electrode 130 is detected by a current detection unit 113 illustrated in FIG. 1 .
  • the value of the current I detected by the current detection unit 113 may be inputted to the controller 60 to be used for the control of the power controller 20 by the controller 60 .
  • a potential difference ⁇ V CA between the reference electrode 112 and the reduction electrode 120 is detected by a voltage detection unit 114 illustrated in FIG. 1 .
  • the value of the potential difference ⁇ V CA detected by the voltage detection unit 114 may be inputted to the controller 60 to be used for the control of the voltage controller 20 by the controller 60 .
  • the reduction electrode 120 is provided in contact with one major surface of the electrolyte membrane 110 .
  • the reduction electrode 120 is a laminated body in which the reduction electrode catalyst layer 122 , the dense layer 142 , and the diffusion layer 140 are laminated in this order from the electrolyte membrane 110 side.
  • the reduction electrode catalyst layer 122 is provided in contact with one major surface of the electrolyte membrane 110 .
  • the reduction electrode catalyst layer 122 includes a reduction catalyst for producing a hydride of an aromatic compound.
  • the reduction catalyst used in the reduction electrode catalyst layer 122 contains at least one of Pt and Pd. Additionally, the reduction catalyst may be composed of a metal composition that contains a first catalyst metal (noble metal) made of at least one of Pt and Pd, and one or two or more second catalyst metals selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Sn, W, Re, Pb, and Bi.
  • the form of the metal composition is an alloy of the first catalyst metal and the second catalyst metal, or an intermetallic compound made of the first catalyst metal and the second catalyst metal.
  • the ratio of the first catalyst metal to the total mass of the first catalyst metal and the second catalyst metals is preferably from 10 to 95 wt %, more preferably from 20 to 90 wt %, and most preferably from 25 to 80 wt %. If the ratio of the first catalyst metal is less than 10 wt %, durability may be deteriorated in terms of resistance to dissolving, and the like.
  • the first catalyst metal and the second catalyst metals may be collectively referred to as a “catalyst metal.”
  • the aforementioned catalyst metal may be supported by an electron conductive material (support).
  • the electron conductivity of the electron conductive material is preferably 1.0 ⁇ 10 ⁇ 2 S/cm or more, more preferably 3.0 ⁇ 10 ⁇ 2 S/cm or more, and most preferably 1.0 ⁇ 10 ⁇ 1 S/cm or more. If the electron conductivity of the electron conductive material is less than 1.0 ⁇ 10 ⁇ 2 S/cm, sufficient electron conductivity may not be imparted.
  • the electron conductive material include electron conductive materials containing any one of porous carbon, a porous metal, and a porous metal oxide as a major component. Examples of the porous carbon include carbon black such as KETJEN BLACK (registered trademark), acetylene black, and VULCANTM.
  • the BET specific surface area of the porous carbon measured by a nitrogen adsorption method, is preferably 100 m 2 /g or more, more preferably 150 m 2 /g or more, and most preferably 200 m 2 /g or more. If the BET specific surface area of the porous carbon is less than 100 m 2 /g, it is difficult to uniformly support the catalyst metal. Accordingly, the rate of utilizing the surface of the catalyst metal is decreased, possibly causing the catalyst performance to be deteriorated.
  • the porous metal include, for example, Pt black, Pd black, a Pt metal deposited in a fractal shape, and the like.
  • porous metal oxide examples include oxides of Ti, Zr, Nb, Mo, Hf, Ta and W.
  • porous electron conductive material for supporting the catalyst metal examples include nitrides, carbides, oxynitrides, carbonitrides, partially-oxidized carbonitrides of metals such as Ti, Zr, Nb, Mo, Hf, Ta, and W (hereinafter, they are collectively referred to as porous metal carbonitrides and the like).
  • the BET specific surface areas of the porous metal, the porous metal oxide, the porous metal carbonitrides and the like, measured by a nitrogen adsorption method, are preferably 1 m 2 /g or more, more preferably 3 m 2 /g or more, and most preferably 10 m 2 /g or more. If the respective BET specific surface areas of the porous metal, the porous metal oxide, the porous metal carbonitrides and the like are less than 1 m 2 /g, it is difficult to uniformly support the catalyst metal. Accordingly, the rate of utilizing the surface of the catalyst metal is decreased, possibly causing the catalyst performance to be deteriorated.
  • a material having electron conductivity such as the aforementioned electron conductive oxide or carbon black, may be added separately from the electron conductive compound for supporting the catalyst metal.
  • the number of electron-conducting paths among reduction catalyst particles can be increased, and hence the resistance per geometric area of a reduction catalyst layer can be lowered in some cases.
  • the reduction electrode catalyst layer 122 may contain, as an additive, a fluorine-based resin such as polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the reduction electrode catalyst layer 122 may contain an ionomer having proton conductivity.
  • the reduction electrode catalyst layer 122 preferably contains, at a predetermined mass ratio, an ion conductive material (ionomer) having a structure that is identical or similar to that of the aforementioned electrolyte membrane 110 . Thereby, the ion conductivity of the reduction electrode catalyst layer 122 can be improved.
  • the catalyst support is porous, the ion conductivity of the reduction electrode catalyst layer 122 is particularly and greatly improved with the reduction electrode catalyst layer 122 containing an ionomer having proton conductivity.
  • Examples of the ionomer having proton conductivity include perfluorosulfonic acid polymers such as NAFIONTM and FLEMIONTM.
  • the ion exchange capacity (IEC) of the cation exchange ionomer is preferably from 0.7 to 3 meq/g, more preferably from 1 to 2.5 meq/g, and most preferably from 1.2 to 2 meq/g.
  • the mass ratio I/C of the cation-exchanging ionomer (I) to the carbon support (C) is preferably from 0.1 to 2, more preferably from 0.2 to 1.5, and most preferably from 0.3 to 1.1.
  • the mass ratio I/C is less than 0.1, it may be difficult to obtain sufficient ion conductivity.
  • the mass ratio I/C is more than 2, the thickness of an ionomer coating over the catalyst metal is increased, and hence the contact of the aromatic compound, a reactant, with a catalyst-active site may be inhibited or the electrode activity may be decreased due to a decrease in the electron conductivity.
  • the reduction catalyst is partially coated with the ionomer included in the reduction electrode catalyst layer 122 .
  • the ionomer included in the reduction electrode catalyst layer 122 .
  • the dense layer 142 is provided, of two major surfaces of the reduction electrode catalyst layer 122 , in contact with one major surface thereof that is opposite to the other major surface that the electrolyte membrane 110 contacts.
  • the dense layer 142 has a function in which a liquid aromatic compound and a hydride of an aromatic compound, which have a relatively low surface tension, are caused to pass through it, while liquid water having a relatively high surface tension is suppressed from passing through it.
  • the diffusion layer 140 is provided, of two major surfaces of the dense layer 142 , in contact with one major surface thereof that is opposite to the other major surface that the reduction electrode catalyst layer 122 contacts.
  • the diffusion layer 140 is formed of a porous material or fiber that causes the liquid aromatic compound and hydride of an aromatic compound, which have been supplied from the later-described separator 150 , to permeate and that has good electron conductivity. Additionally, it is preferable that the material that forms the diffusion layer 140 has a high affinity with the aforementioned aromatic compounds.
  • the material that forms the diffusion layer 140 for example, carbon paper, and woven cloth or non-woven cloth of carbon, etc., can be used.
  • the thickness of the diffusion layer 140 is preferably from 50 to 1000 ⁇ m, and more preferably from 100 to 500 ⁇ m. Additionally, it is preferable that the electron conductivity of the material that forms the diffusion layer 140 is 10 ⁇ 2 S/cm or more.
  • a material can be used for the diffusion layer 140 , in which fine particles of a corrosion-resistant alloy such as Cr—Mo are solidified.
  • a treatment such as a water repellent treatment, lipophilic treatment, or the like.
  • the dense layer 142 is formed, for example, by coating a kneaded product in a paste state, which is obtained by kneading an electron conductive powder and a water repellent, to the diffusion layer 140 so as to fill the void thereof and then by drying it.
  • Conductive carbon such as VULCANTM can be used as the electron conductive powder.
  • a fluorine resin such as a tetrafluoroethylene resin (PTFE) can be used as the water repellent.
  • the ratio of the electron conductive powder to the water repellent can be appropriately determined to be within a range in which desired electron conductivity and water repellency are obtained, but when VULCANTM and PTEE are used as the electron conductive powder and the water repellent, respectively, the ratio is, for example, from 4:1 to 1:1 (VULCAN:PTEE).
  • the mean flow pore diameter (dm) of the dense layer 142 is preferably from 100 nm to 20 ⁇ m, and more preferably from 500 nm to 5 ⁇ m. Additionally, the thickness of the dense layer 142 is preferably from 1 to 50 ⁇ m, and more preferably from 2 to 20 ⁇ m. When the dense layer 142 is formed to be recessed from the surface of the diffusion layer 140 , the average thickness of the dense layer 142 itself, including the portion recessed into the diffusion layer 140 , is defined to be the thickness.
  • the dense layer 142 on one major surface of the reduction electrode catalyst layer 122 By providing the dense layer 142 on one major surface of the reduction electrode catalyst layer 122 , the one major surface being opposite to the other major surface thereof that the electrolyte membrane 110 contacts, water can be easily retained in a proton conductive portion such as the ionomer (electrolyte) in the reduction electrode catalyst layer 122 and the cathode side of the electrolyte membrane 110 . Thereby, the proton reduction reaction at the reduction electrode 120 side can be facilitated more easily in an environment in which a large amount of organic substances such as aromatic compounds are present.
  • the separator 150 is laminated on one major surface of the diffusion layer 140 , the one major surface being opposite to the electrolyte membrane 110 .
  • the separator 150 is formed of a carbon resin, or a corrosion-resistant alloy such as Cr—Ni—Fe, Cr—Ni—Mo—Fe, Cr—Mo—Nb—Ni, or Cr—Mo—Fe—W—Ni.
  • One or more groove-like flow channels 152 are provided in the surface of the separator 150 on the diffusion layer 140 side.
  • the liquid aromatic compound supplied from the organic substance storage tank 30 circulates through the flow channel 152 , and the liquid aromatic compound permeates the liquid diffusion layer 140 from the flow channel 152 .
  • the form of the flow channel 152 is not particularly limited, but for example, a straight flow channel or a serpentine flow channel can be employed.
  • the separator 150 may have a structure formed by sintering sphere-like or pellet-like metal fine powders.
  • the oxygen generating electrode 130 is provided in contact with the other major surface of the electrolyte membrane 110 .
  • the oxygen generating electrode 130 contains, as a catalyst, one or two or more metals or metal oxides, the metal (metals) being selected from the group consisting of Ru, Rh, Pd, Ir, and Pt.
  • These catalysts may be dispersedly supported or coated by or on a metal substrate having electron conductivity such as: a metal fiber (fiber diameter: e.g., from 10 to 30 ⁇ m) of a metal or an alloy whose major components are metals, the metal or metals being selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta, and W; a mesh (diameter: e.g., from 500 to 1000 ⁇ m); a sintered body of a porous metal; a foamed molded body (form); an expanded metal; or the like.
  • a metal fiber fiber diameter: e.g., from 10 to 30 ⁇ m
  • a metal or an alloy whose major components are metals, the metal or metals being selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ta, and W
  • a mesh diameter: e.g., from 500 to
  • the thickness of the catalyst layer is preferably from 0.1 to 10 ⁇ m, and more preferably from 0.2 to 5 ⁇ m.
  • the surface of the metal substrate may be covered with an electron conductive protective layer made of one or two or more metals or metal oxides, the metal (metals) being selected from the group consisting of Nb, Mo, Ta, and W.
  • the thickness of the protective layer is preferably from 0.05 to 2 ⁇ m, and more preferably from 0.1 to 1 ⁇ m.
  • the metal substrate plays a role as a substrate for holding the catalyst, and also functions as a current collecting member.
  • FIG. 4 is a schematic view illustrating an enlarged example of a sectional structure of the oxygen generating electrode 130 .
  • a catalyst 136 is held on the surface of a protective layer 134 covering a metal substrate 132 .
  • the metal substrate 132 is an expanded metal formed of a metal material such as Ti.
  • the protective layer 134 is formed of one or two or more metals or metal oxides, the metal (metals) being selected from the group consisting of Nb, Mo, Ta, and W.
  • the catalyst 136 is formed of one or two or more metals or metal oxides, the metal (metals) being selected from the group consisting of Ru, Rh, Pd, Ir, and Pt.
  • the current collector 160 electrically connected to the aforementioned oxygen generating electrode 130 is provided in the electrode unit 100 .
  • the current collector 160 has a substrate portion 162 and a connection portion 164 , both formed of a metal having good electron conductivity, such as copper or aluminum.
  • the substrate portion 162 is a planar metal member installed so as to be spaced apart from the oxygen generating electrode 130 by a predetermined distance.
  • the space between the substrate portion 162 and the oxygen generating electrode 130 is used for the circulation of the water supplied to the oxygen generating electrode 130 .
  • connection portion 164 of the present embodiment is a strip-shaped metal member whose short side is curved.
  • a plurality of the connection portions 164 are provided in combination so as to be spaced apart from each other by predetermined intervals in a state in which one long side of each connection portion 164 is fixed to the substrate portion 162 .
  • the other long side thereof is electrically connected to the oxygen generating electrode 130 .
  • Each connection portion 164 and the oxygen generating electrode 130 may be fixed by welding, etc. Because the connection portion 164 has a shape in which the short side is curved, it can play a role of a spring. Accordingly, the contact between the connection portion 164 and the oxygen generating electrode 130 can be made more reliable by pressing the substrate portion 162 toward the oxygen generating electrode 130 .
  • the connection portion 164 is strip-shaped in the present embodiment, but the shape of the connection portion 164 is not limited thereto.
  • the connection portion 164 may be formed, for example, by a spring-like wire, etc.
  • liquid water is supplied to the oxygen generating electrode 130 , but humidified gas (for example, air) may be used instead of liquid water.
  • humidified gas for example, air
  • the dew-point temperature of the humidified gas is preferably from room temperature to 100° C., and more preferably from 50 to 100° C.
  • reactions in the electrode unit 100 are as follows.
  • the electrode reaction at the oxygen generating electrode and that at the reduction electrode proceed in parallel, and the protons generated by the electrolysis of water occurring due to the electrode reaction at the oxygen generating electrode 130 is supplied to the reduction electrode 120 via the electrolyte membrane 110 .
  • the proton supplied to the reduction electrode 120 is used for producing a hydride of an aromatic compound in the electrode reaction at the reduction electrode 120 .
  • an aromatic compound is uniformly and quickly supplied to a reaction site of the reduction electrode catalyst layer 122 and a hydride of the aromatic compound is promptly removed from the reaction site, by providing the diffusion layer 140 .
  • the hydride-producing reaction for an aromatic compound can be promoted.
  • a decrease in the hydride-producing reaction for the aromatic compound can be suppressed.
  • a certain amount of moisture can be retained in the reduction electrode catalyst layer 122 by providing the dense layer 142 between the diffusion layer 140 and the reduction electrode catalyst layer 122 , and hence the electrolyte membrane 110 and the reduction electrode catalyst layer 122 are suppressed from being dried and the hydride-producing reaction for an aromatic compound can be further promoted.
  • the configurations of respective electrode units of Examples from 1 to 5 and Comparative Example 1 are shown in Table 1.
  • the respective electrode units were evaluated by using toluene as an aromatic compound. Differences among the respective electrode units of Examples from 1 to 5 and Comparative Example 1 are as follows: That is, the electrode units of Examples from 1 to 5 have a dense layer, while that of Comparative Example 1 does not have a dense layer.
  • the mean flow pore diameters of the dense layers of Examples from 1 to 5 were set to be 3.2 ⁇ m, 1.1 ⁇ m, 0.76 ⁇ m, 1 ⁇ m, and 23 ⁇ m, respectively.
  • the electron conductive powders of the dense layers of Examples from 1 to 5 were VULCANTM, and the water repellents thereof were PTFE.
  • the ratio of the VULCAN to the PTEE was set to be 1:1 in Examples 1, 2, 4, and 5, and that was set to be 4:1 in Example 3.
  • the thicknesses of the dense layers of Examples from 1 to 5 were set to be 8.6 ⁇ m, 8.5 ⁇ m, 8.4 ⁇ m, 0.76 ⁇ m, and 9.6 ⁇ m, respectively.
  • EXAMPLE 1 EXAMPLE 2
  • FIG. 5 is a graph showing I-V curves obtained by the respective electrode units of Examples from 1 to 5 and Comparative Example 1. As shown in FIG. 5 , it has been confirmed that, when the potential differences between the reduction electrode and the reference electrode are made the same as each other, the absolute values of the current densities are further increased in Examples from 1 to 5, in comparison with that in Comparative Example 1. It has been confirmed that the absolute values of the current densities are remarkably increased particularly in Examples from 1 to 3.
  • the concentration of the toluene supplied to the reduction electrode was detected under a condition in which the absolute value of the current density was set to be 50 mA/cm 2 .
  • a converted substance amount was determined from a change in the toluene concentration by using gas chromatography.
  • an electricity amount was determined from the time integration of current time transition in each of the electrochemical measurement devices. Then, with the converted substance amount being divided by the electricity amount, Faraday efficiency was calculated. The obtained results with respect to the Faraday efficiencies are shown in Table 2.
  • the absolute value of the current density at a boundary point point indicated by mark “X” in FIG.
  • a separator including a diffusion layer for uniformly diffusing water to the oxygen generating electrode 130 and a flow channel for circulating water to be supplied to the oxygen generating electrode 130 , may be installed on the side of the oxygen generating electrode 130 similarly to the side of the reduction electrode 120 , instead of the current collector 160 .
  • An electrochemical reduction device comprising:
  • a reduction electrode including a reduction electrode catalyst layer that is provided in contact with one major surface of the electrolyte membrane and has an electron conductive material and a metal containing one or both of Pt and Pd supported by the electron conductive material, a diffusion layer that is provided near to the other major surface of the reduction electrode catalyst layer, the other major surface being opposite to the electrolyte membrane, and that causes a liquid aromatic compound and a hydride of the aromatic compound to pass through, and a dense layer provided between the diffusion layer and the reduction electrode catalyst layer;
  • an oxygen generating electrode provided in contact with the other major surface of the electrolyte membrane
  • a power controller that externally applies an electric field such that the reduction electrode has an electronegative potential and the oxygen generating electrode has an electropositive potential.
  • a mean flow pore diameter of the dense layer is 20 ⁇ m or less.
  • a thickness of the dense layer (t) is 1 ⁇ m ⁇ t ⁇ 50 ⁇ m.
  • the dense layer contains a mixture of an electron conductive powder and a water repellent.
  • a mass ratio of the electron conductive powder to the water repellent in the mixture is 4 or more.
  • the diffusion layer has a fiber-like shape or a shape in which many particles are solidified.
  • the diffusion layer contains a carbon fiber.
  • the diffusion layer contains a material having an electron conductivity of 1.0 ⁇ 10 ⁇ 2 S/cm or more.

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KR20190077531A (ko) * 2016-11-15 2019-07-03 고쿠리츠다이가쿠호진 요코하마 고쿠리츠다이가쿠 유기 하이드라이드 제조장치 및 유기 하이드라이드의 제조방법
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JP6954561B2 (ja) * 2017-05-23 2021-10-27 国立大学法人横浜国立大学 有機ハイドライド製造装置
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