CN117355638A - CO 2 Electrolysis device and CO 2 Method for producing electrolytic product - Google Patents

CO 2 Electrolysis device and CO 2 Method for producing electrolytic product Download PDF

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Publication number
CN117355638A
CN117355638A CN202280035394.7A CN202280035394A CN117355638A CN 117355638 A CN117355638 A CN 117355638A CN 202280035394 A CN202280035394 A CN 202280035394A CN 117355638 A CN117355638 A CN 117355638A
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China
Prior art keywords
anion exchange
catalyst
exchange resin
ionomer
present disclosure
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Inventor
宫武健治
横田尚树
永濑胜也
兼古宽之
冈本裕二
贾庆鑫
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Idemitsu Kosan Co Ltd
Takahata Precision Co Ltd
University of Yamanashi NUC
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Idemitsu Kosan Co Ltd
Takahata Precision Co Ltd
University of Yamanashi NUC
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • 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
    • C25B11/054—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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Providing a catalyst consisting of CO 2 CO having more excellent production efficiency of reduction product (CO, etc.) is produced 2 Related art of electrolyzer and CO suppression 2 Reduction efficiency is reduced and stable operation of CO can be realized 2 Related art electrolytic devices. One mode of the invention is a CO 2 Electrolytic device, itsHas an electrode material. The CO 2 The electrolysis apparatus comprises a support comprising a conductive support and a catalyst supported on the conductive support and comprising any one or more of metal complex particles, metal particles or inorganic compound particles, and an anion exchange resin covering a part or the whole of the surface of the support and comprising an ionomer of the following formula (1). (wherein m and n represent natural numbers of 1 to 200)

Description

CO 2 Electrolysis device and CO 2 Method for producing electrolytic product
Technical Field
The present disclosure relates to CO 2 Electrolysis device and CO 2 A method for producing an electrolytic product.
Background
Fossil fuels (petroleum, coal, natural gas) support modern energy consumption society. With CO when energy is extracted from fossil fuels 2 (carbon dioxide) emissions. One of the causes of the rise in the carbon dioxide concentration in the atmosphere is called global warming, and reduction thereof is demanded. CO 2 Since it is extremely stable, it is difficult to reuse it by decomposition or the like, and it is required to use it for CO 2 New technology for converting into other substances and recycling the substances again.
As one of the technologies, CO is performed using electric energy widely worldwide 2 Is a study of (a). And find out: CO having polyelectrolyte-type electrolysis cell 2 The reduction device uses a thin-film polyelectrolyte, and thus has an advantage over other devices in that ion movement resistance can be sufficiently reduced (patent document 1). Generally, CO used in a polyelectrolyte-type electrolysis cell 2 The reduction cathode contains catalyst particles and a conductive carrier.
In CO 2 In the reduction, CO 2 Reduction of CO in the vicinity of a catalyst 2 The adsorption amount significantly contributes to the efficiency of formation of reduction products such as CO (carbon monoxide), and development of a catalyst capable of adsorbing CO in a large amount is desired 2 Is a catalyst for an electrode. The following methods are contemplated, for example: by supporting the catalyst on the electrode together with the catalyst, the catalyst has a catalyst activity of CO 2 Compounds exhibiting such a property that adsorption or the like is effected to thereby enhance CO exhibiting weak acidity 2 The adsorption amount of (a) improves the production efficiency (patent documents 2 and 3 and non-patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2019-515142
Patent document 2: japanese patent application laid-open No. 2019-01492
Patent document 3: japanese re-public publication No. 2019-65258
Non-patent literature
Non-patent document 1: S.Ren, D.Joulie, D.Salvatore, K.Torbensen, M.Wang, M.Robert, C.P.Berlinguette, science,2019,365,367-369.
Disclosure of Invention
Problems to be solved by the invention
In the invention disclosed in patent document 1, various ion exchange membranes have been proposed as a film-like polymer electrolyte. The ion exchange membrane for such applications is required to have high ion conductivity, high toughness, high chemical resistance, heat resistance, and appropriate water content, but the ion exchange membrane proposed in patent document 1 may be insufficient. For example, in the case of low ionic conductivity, CO may be involved 2 The transport efficiency of ions consumed or generated by the electrolytic reduction reaction is lowered, resulting in a decrease in the reaction rate. In addition, when toughness, chemical resistance, and heat resistance are insufficient, the electrode may not be CO-resistant 2 Reaction conditions for the reduction. Further, when the ion exchange membrane has low selective permeability and high water content, there is a possibility that the electrolyte solution may permeate from the anode side and overflow to the cathode side. Further, the electrolyte may also form salts and precipitate. These phenomena can interfere with CO 2 Is supplied with and initiates CO 2 Reduction efficiency is lowered, and thus, becomes an obstacle to CO 2 One reason for the stable operation of the electrolyzer.
The inventions disclosed in patent documents 2 and 3 are directed to CO supplied thereto 2 Partial pressure (i.e. CO) 2 Concentration) is reduced, it may be difficult to convert low concentration CO 2 A large amount of the catalyst is kept near the reduction catalyst, and the reduction product is generated efficiently and CO 2 CO of electrolysis apparatus 2 The conversion decreases.
In addition, in the case where a carbon dioxide reduction membrane containing a proton-permeable polymer as a cation exchange resin is used for the cathode electrode as in the carbon dioxide reduction apparatus disclosed in patent document 2, side reactions (hydrogen generation reaction and progress easily under acidic conditions) are likely to occur because the cation exchange resin is acidic. Furthermore, since the cation exchange resin is acidic, no CO is present 2 Adsorption capacity, there is a possibility that the ionic conductivity and CO may not be compatible 2 Adsorption capacity, which is shown in reference example 5 (paragraph 0061) of patent document 2 by adding N as a cation exchange resinThe afion leads to CO 2 The data of the decrease in the adsorption amount of (a) can be clarified.
Further, since the cation exchange resin permeates metal ions, precipitation of electrolyte salts is likely to occur, and if the precipitated salts are accumulated, the carbon dioxide electrolysis efficiency may be lowered.
Accordingly, an object of the present disclosure is to provide a method for producing a catalyst from CO 2 CO having more excellent production efficiency of reduction product (CO, etc.) is produced 2 Related art electrolytic devices. Further, it is an object to provide a method for suppressing CO 2 Reduction efficiency is reduced and stable operation of CO can be realized 2 Related art electrolytic devices.
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the anion exchange resin is basic and is less likely to cause the aforementioned side reactions: the above-described problems can be solved by using a carrier comprising a catalyst and a conductive carrier, which is covered with a specific anion exchange resin, as an electrode material. It was additionally found that: the above problems can be solved by using an anion exchange membrane obtained by using the same anion exchange resin as a film-like polymer electrolyte (solid electrolyte), thereby satisfying the requirements of a film-like polymer electrolyte having high ion conductivity, high permselectivity, high toughness, high chemical resistance, heat resistance, moderate water content, and the like. Thus completing the techniques of the present disclosure. That is, the technology of the present disclosure is as follows.
According to one aspect of the present disclosure, is a CO 2 An electrolysis device having an electrode material comprising a carrier and an anion exchange resin,
the carrier comprises a conductive carrier and a catalyst which is carried on the conductive carrier and comprises any one or more of metal complex particles, metal particles or inorganic compound particles,
the anion exchange resin covers a part or the whole of the surface of the aforementioned support and contains an ionomer of the following formula (1).
[ chemical 1]
(wherein m and n represent natural numbers of 1 to 200)
Effects of the invention
According to the present disclosure, a method of producing a CO gas from a CO gas stream 2 Electrode material excellent in efficiency of producing reduction product (CO, etc.), and CO-suppressing agent 2 Membrane-electrode assembly and CO capable of stable operation with reduced reduction efficiency 2 Related art electrolytic devices.
Drawings
FIG. 1 is a schematic diagram illustrating a CO suitable for use in the present disclosure 2 An example of a schematic diagram of an electrolytic device.
Fig. 2 is a schematic diagram illustrating a material for an electrode in the present disclosure.
Fig. 3 is an example of a schematic diagram illustrating a membrane-electrode assembly suitable for use in the present disclosure.
Detailed Description
The following is directed to CO in the present disclosure 2 The electrolytic device is specifically described. The invention described in the present disclosure is not limited to the embodiments described below.
CO of the present disclosure 2 The electrolytic device includes an electrode material. By using the electrode material of the present disclosure as a cathode, CO can be obtained 2 Excellent reduction efficiency, especially in CO supplied 2 More efficient CO at low concentrations 2 An electrolysis device. CO 2 The electrolysis device can be used for CO such as CO 2 A method for producing an electrolytic product.
CO for the present disclosure 2 An example of an electrolyzer will be described with reference to FIG. 1. CO 2 The electrolysis apparatus comprises: a cathode 101, an anode 102 forming a pair of electrodes with the cathode 101, a solid electrolyte 103 interposed between the cathode 101 and the anode 102 in at least partial contact, a current collector 104 in contact with the surface 101-2 of the cathode 101 opposite to the contact surface 101-1 in contact with the solid electrolyte 103, and a solid electrolyte 103 in contact with the anode 102A support plate 105 in contact with the surface 102-1 on the opposite side of the contact surface 102-2, and a voltage applying section 106 for applying a voltage between the current collector 104 and the support plate 105 (i.e., between the cathode and the anode). Further, CO in a gas phase state is supplied by a supply source and a supply device, not shown 2 H as supporting electrolyte 2 O、KHCO 3 And an aqueous electrolyte solution. The CO shown in FIG. 1 2 The electrolytic device 100 is illustrated in a state in which the components such as the cathode 101 and the anode 102 are separated for the sake of explanation, but in reality, the current collector 104, the cathode 101, the solid electrolyte 103, the anode 102, and the support plate 105 are integrally formed by bonding them by a predetermined method. The components are configured in a detachable manner, and can form a CO 2 An electrolysis apparatus 100.
Here, the electrode material described in the present disclosure is used for the cathode 101.
The membrane-electrode assembly according to the present disclosure functions as the current collector 104, the cathode 101, and the solid electrolyte 103 in fig. 1. That is, the current collector constituting the membrane-electrode assembly is the current collector 104, the electrode material described in the present disclosure is the cathode 101, and the solid electrolyte 103 is constituted by the anion exchange membrane, so that an integrated cathode can be formed.
Hereinafter, an electrode material according to the present disclosure will be described.
1. Electrode material
The electrode material according to the present disclosure is an electrode material comprising a catalyst, a conductive support, and an anion exchange resin. The catalyst is supported on a conductive carrier, which forms a carrier. The anion exchange resin covers a part or the whole of the surface of the carrier (see fig. 2).
1-1. Conductive Carrier
The conductive carrier described in the present disclosure comprises a carbon material, titanium, tantalum, gold, silver, or copper. These may be used singly or in combination. They may be selected in consideration of corrosion resistance.
Here, the carbon material is not particularly limited as long as it has conductivity and does not hinder the effect of the technology of the present disclosure. As the carbon material, materials known to be used for electrode materials can be used, and for example, graphitic carbon, glassy carbon, carbon black, graphene, carbon nanotubes, and the like can be used.
The conductive carrier is granular or short fiber. The conductive carrier may be an aggregate obtained by aggregating particles (primary particles) or short fibers. The term "particulate form" or "staple fiber form" as used herein refers to a form of particulate form or staple fiber form as determined by common general knowledge. In addition, in the present disclosure, aggregates obtained by aggregation of short fibers are also included in the secondary particles.
The average particle diameter of the particles of the conductive carrier or the average fiber length of the short fibers is not particularly limited as long as the effect of the technology of the present disclosure is not hindered, and may be set to, for example, 10nm to 1000 μm. The average particle diameter and average fiber length of the conductive support may be selected in consideration of the surface area and the porosity of the conductive support. Here, the average particle diameter refers to an average particle diameter including primary particles or short fibers and including secondary particles. Here, when the conductive support is in the form of a staple fiber, the average particle diameter is a value obtained by averaging the primary particle diameter obtained by taking the fiber length of the staple fiber as the primary particle diameter and the particle diameter of the secondary particle of the staple fiber. In the measurement of the average particle diameter, the diameter of 50 particles selected at random is measured by a known observation means such as an optical microscope, a scanning electron microscope, or a transmission electron microscope, and the average value is calculated, whereby the measurement can be performed. The observation means may be selected according to the average particle diameter.
1-2 catalyst
The catalyst described in the present disclosure is supported on a conductive carrier to form a carrier.
The catalyst is a known catalyst capable of reducing carbon dioxide, and contains particles of metals or inorganic compounds such as gold, silver, copper, nickel, iron, cobalt, zinc, chromium, palladium, tin, manganese, aluminum, indium, bismuth, molybdenum, tin oxide, copper oxide, or carbon nitride; or particles of a metal complex of copper, nickel, iron, cobalt, zinc, manganese, molybdenum, rhenium, tin, indium, lead, ruthenium, or aluminum. These may be used singly or in combination. In addition, they may be selected in consideration of corrosion resistance.
The catalyst is mainly granular. The catalyst may be secondary particles obtained by aggregation of particles (primary particles). The term "particulate" is not limited to the form of particles determined by common general knowledge, but includes a form in which the catalyst is very small and the coordination-bonded metal called "monoatomic catalyst" is highly dispersed at an atomic level.
The average particle diameter of the catalyst particles is not particularly limited as long as the effect of the technology of the present disclosure is not impaired, and may be set to, for example, 0.001 to 100 μm, preferably 0.001 to 1 μm, and more preferably 0.001 to 0.1 μm. The particle size of the catalyst may be selected freely taking into account the surface area of the catalyst and the size effect of the catalyst. The larger the particle diameter of the catalyst, the larger the surface area of the catalyst, and thus, there is an effect that the catalyst has a larger number of active sites (sites) contributing to the reaction. On the other hand, according to the particle diameter of the catalyst, unlike the effect of the surface area, there is also an effect that the activity and selectivity are significantly changed, which is called a size effect. Therefore, depending on the apparatus used, the activity of the catalyst may be confirmed and the particle size of the catalyst may be selected. The average primary particle diameter of the catalyst involved in the reduction reaction of carbon dioxide is preferably 50nm or less, more preferably 20nm or less, in the technique of the present disclosure, as the average primary particle diameter of the catalyst becomes smaller and more effective. In addition, when the catalyst is dispersed without aggregation, that is, when the amount of primary particles contained is large, the effect of the catalyst is high, and therefore, the catalyst is suitable. Herein, the average particle diameter of the catalyst means an average particle diameter including primary particles and secondary particles of the catalyst. The average primary particles mean average primary particle diameter of only primary particle diameter. For measurement of these average (or primary) particle diameters, the diameters of 50 particles (or primary particles) selected at random are measured using a known observation device such as an optical microscope, a scanning electron microscope, or a transmission electron microscope, and the average value is calculated, whereby measurement can be performed. The observation means may be selected based on the average (or primary) particle size.
The amount of the catalyst supported on the conductive carrier is not particularly limited as long as the effect of the technology of the present disclosure is not impaired, and for example, when the total amount of the carrier is 100 mass%, the amount of the catalyst supported on the carrier may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, and 70 mass% or less, 60 mass% or less, or 50 mass% or less. When the catalyst loading falls within this range, catalyst aggregation can be suppressed, and the catalytic activity can be maintained high.
1-3 anion exchange resin
The anion exchange resin described in the present disclosure covers a portion or all of the surface of a support comprising a catalyst and a conductive support.
The anion exchange resin described in the present disclosure is an ionomer of the following formula (1).
[ chemical 2]
(wherein m and n represent natural numbers of 1 to 200)
The ion exchange resin (ionomer) is 0.5mmol/g or more and 3.5mmol/g or less, preferably 1.0mmol/g or more and less than 2.5mmol/g. In the case where the ion exchange capacity of the anion exchange resin falls within this range, a resin having excellent CO can be obtained 2 Electrode material with reduction efficiency.
When the carrier obtained by loading the catalyst on the conductive carrier is not covered with the anion exchange resin, even when the carrier is covered with the anion exchange resin, the ion exchange capacity of the anion exchange resin is low, CO 2 The presence of ions generated by the reduction reaction or to be consumed may reduce the energy and mobility, and thus the reduction reaction rate may be reduced. In addition, due to CO supplied to the electrode material 2 Is a gas, and thus, CO 2 Can freely move, CO 2 Limited opportunity for adsorption to the active sites of the catalyst, CO 2 Reduction efficiency is also limited.
On the other hand, on the supportWhen the body is covered with the anion exchange resin of the formula (1), it is preferable that the ion exchange capacity of the anion exchange resin of the formula 1 is further increased to a certain value or more (the ion exchange capacity is 1.0mmol/g or more), because of CO 2 The presence of ions generated by the reduction reaction or to be consumed may increase the energy and conductivity, and the reduction reaction rate can be increased. In addition, CO as a weak acid incorporated into the cover 2 Is neutralized by the alkali sites of the anion exchange resin and can be mainly prepared by the reaction of bicarbonate ions (HCO 3 - ) Or carbamate (carbamate) form, is retained within the anion exchange resin. As a result, bicarbonate ions are stored in the vicinity of the catalyst supported on the carrier, and the bicarbonate ions form CO by the equilibrium reaction 2 Thereby, CO 2 Can be efficiently adsorbed to the active site of the catalyst. This can improve CO of the electrode material 2 Reduction efficiency. The effect is that of CO supplied 2 The method is effective even when the concentration is high, but is effective when CO is supplied 2 This is more effective at low concentrations.
In addition, when the ion exchange capacity exceeds 3.5mmol/g, the hydrophilicity becomes high, and therefore, there is a possibility that water (H) generated during the neutralization reaction 2 O) is swelled by CO 2 Is blocked and undergoes a side reaction 2 Generated, or as CO 2 The mechanical properties of the electrode material become low.
The ion exchange capacity of the anion exchange resin can be adjusted according to the ratio of the hydrophobic structure to the hydrophilic structure within the molecular structure of the ionomer.
Here, the hydrophobic structure refers to a moiety represented by the following formula (2) in formula (1).
[ chemical 3]
The hydrophilic structure refers to a moiety represented by the following formula (3) in formula (1).
[ chemical 4]
Further, the ratio of the hydrophobic structure to the hydrophilic structure within the molecular structure of the ionomer may be shown as n/m using m and n of formula 1. By adjusting this ratio, the ion exchange capacity of the ionomer can be adjusted.
In the above-mentioned formulae, the repeating structural parts of the hydrophobic structure and the hydrophilic structure are shown by brackets, but the repeating structure is not limited to the structure (block polymer) in which the repeating structures are polymerized into a block, and may be a structure in which the repeating structures are bonded to each other in a random, alternating, or other regular manner.
Therefore, as a method for adjusting the ion exchange capacity of the anion exchange resin, the polymer obtained by polymerizing the monomer in advance and the polymer obtained by polymerizing the monomer in advance, which are the polymer having a hydrophilic structure, can be adjusted by adjusting the respective compounding ratios (m/n) and copolymerizing them.
The ion exchange capacity of the anion exchange resin is obtained from the integral value of the signal of the quaternary ammonium group and other functional groups that become base sites, as measured by 1H-NMR.
The anion exchange resin covers a part or the whole of the surface of the support, and the ratio of the coverage area of the support to the surface area, that is, the coverage (coverage area/support surface area×100) may be 70% or more, 80% or more, 90% or more, 95% or more, or 100%. From the large amount of CO 2 From the viewpoint of the effect of accumulating in the vicinity of the catalyst, a high coverage is preferable. Here, the coverage is set as: the particle surfaces of the randomly selected 50 electrode materials were observed by a transmission electron microscope, and the average value of the coverage was calculated by the above formula.
The average thickness of the anion exchange resin is not particularly limited as long as the effect of the technology of the present disclosure is not impaired, and may be set to 0.01 to 100 μm, for example.
If anion exchange resinsWhen the average coating thickness is 0.01 μm or more, ion-conducting channels are sufficiently formed, and hydroxide ions (OH) generated by the reaction can be formed - ) More efficient transport to the ion exchange membrane and sufficient alkali site amount, CO 2 The amount of the carbonate species such as bicarbonate ion to be retained becomes sufficient.
In addition, when the average coating thickness of the anion exchange resin is 100 μm or less, the distance that the ions must travel becomes appropriate, and therefore, the resistance against the movement of the ions becomes appropriate, and an increase in voltage (decrease in suppression efficiency) can be suppressed. Further, CO 2 The distance that must be diffused in order to reach the catalyst is not excessive, therefore, CO 2 Easy movement, and can suppress voltage increase (suppression efficiency reduction).
In summary, when the average coverage of the anion exchange resin falls within this range, a catalyst composed of CO can be obtained 2 Excellent efficiency of producing reduction products (CO, etc.), especially in CO 2 In the case of a low supply concentration, the production efficiency of the reduced product is more excellent.
2. Method for producing electrode material
2-1. Synthesis of anion exchange resins (ionomers)
Examples of suitable synthetic methods for anion exchange resins (ionomers) according to the disclosed technology are described. The technology of the present disclosure is not limited at all to the following synthetic methods.
2-1-1 Synthesis of monomer 1
1, 6-Diiodoperfluorohexane (e.g., 10.0 mmol), 3-chloroiodobenzene (e.g., 50 mmol), and N, N-dimethyl sulfoxide (e.g., 60 mL) were added to a round-bottom three-necked flask equipped with a nitrogen inlet and a condenser. After the mixture was stirred to prepare a homogeneous solution, copper powder (e.g., 150 mmol) was added thereto, and the reaction was carried out at 120℃for 48 hours. The reaction solution was added dropwise to a 0.1M aqueous nitric acid solution to stop the reaction. The precipitate recovered from the mixture by filtration was washed with methanol, and the filtrate was recovered. After repeating the same operation, pure water was added to the combined filtrate, the white solid precipitated thereby was collected by filtration, washed with a mixed solution of pure water and methanol (pure water/methanol=1/1), and then dried under vacuum (60 ℃) overnight, whereby monomer 1 (white solid) represented by the following formula (4) was synthesized.
[ chemical 5]
2-1-2 Synthesis of monomer 2
Fluorene (e.g., 0.50 mol), N-chlorosuccinimide (e.g., 1.25 mol), acetonitrile (e.g., 166 mL) were added to a round bottom three-necked flask. After the mixture was stirred to prepare a homogeneous solution, 12M hydrochloric acid (for example, 16.6 mL) was added, and the reaction was performed at room temperature for 24 hours. The precipitate recovered from the reaction solution by filtration was washed with methanol and pure water, and then dried under vacuum (60 ℃) overnight, whereby monomer 2 (white solid) represented by the following formula (5) was obtained.
[ chemical 6]
2-1-3 Synthesis of monomer 3
To a round bottom three neck flask was added monomer 2 (e.g., 35.0 mmol), 1, 6-dibromohexane (e.g., 53 mL). After the mixture was stirred to prepare a homogeneous solution, a mixed solution of tetrabutylammonium (e.g., 7.00 mmol), potassium hydroxide (e.g., 35.0 g), and pure water (e.g., 35 mL) was added thereto, and the reaction was performed at 80℃for 1 hour. Pure water was added to the reaction solution to stop the reaction. The target substance was extracted from the aqueous layer with methylene chloride, and the combined organic layers were washed with pure water and brine, followed by distillation of water, methylene chloride and 1, 6-dibromohexane. The crude product was purified by silica gel column chromatography (developing solvent: dichloromethane/hexane=1/4), and then dried under vacuum (60 ℃) overnight, whereby monomer 3 (pale yellow solid) represented by the following formula (6) was obtained.
[ chemical 7]
2-1-4 Synthesis of monomer 4
To a round bottom three-necked flask was added monomer 3 (e.g., 23.4 mol), tetrahydrofuran (e.g., 117 mL). After the mixture was stirred to prepare a homogeneous solution, a 40wt% aqueous solution of dimethylamine (e.g., 58.6 mL) was added, and the reaction was performed at room temperature for 24 hours. Saturated aqueous sodium hydrogencarbonate solution was added to the reaction solution to stop the reaction. After removal of tetrahydrofuran, hexane was added to extract the target component. The organic layer was washed with brine, and then water and hexane were distilled off. By drying it at 40℃under vacuum overnight, monomer 4 (pale yellow solid) represented by the following formula (7) can be obtained.
[ chemical 8]
2-1-5 polymerization
To a round-bottom three-necked flask equipped with a nitrogen inlet and a condenser was added monomer 1 (e.g., 2.91 mmol), monomer 4 (e.g., 1.67 mmol), 2' -bipyridine (e.g., 10.9 mmol), and N, N-dimethylacetamide (e.g., 11 mL). After the mixture was stirred to prepare a homogeneous solution, bis (1, 5-cyclooctadiene) nickel (0) (e.g., 10.9 mmol) was added and reacted at 80℃for 3 hours. The reaction mixture was added dropwise to a mixed solution of methanol and 12M hydrochloric acid (methanol/12M hydrochloric acid=1/1) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with 12M hydrochloric acid, 0.2M aqueous potassium carbonate solution and pure water, and then dried under vacuum (60 ℃) overnight, whereby an anion exchange resin precursor polymer (yellow solid) represented by the following formula (8) was obtained.
[ chemical 9]
2-1-6 quaternization reaction
To a round bottom three-necked flask was added an anion exchange resin precursor polymer (e.g., 1.70 g), N-dimethylacetamide (e.g., 9.6 mL). After the mixture was stirred to prepare a homogeneous solution, methyl iodide (e.g., 7.22 mmol) was added thereto, and the reaction was carried out at room temperature for 48 hours. The reaction solution to which N, N-dimethylacetamide (e.g., 10 mL) was added was filtered. The filtrate was poured onto a glass plate bordered with silicone rubber and dried on a heated plate (50 ℃) adjusted to horizontal. After the film was washed in pure water (e.g., 2L), it was dried under vacuum (60 ℃) overnight, thereby obtaining a pale-tea-colored transparent film. Further, the solution was immersed in a 1M aqueous potassium hydroxide solution for 48 hours, and then washed with degassed pure water, whereby the counter ion of the ion exchange group (quaternary ammonium group) was converted from iodide ion to hydroxide ion. Thus, an anion exchange resin (ionomer) represented by the following formula (1) can be obtained (for example, when m/n=1/0.60, ion exchange capacity=1.47 mmol/g). In addition, the obtained anion exchange resin is formed into a membrane, whereby an anion exchange membrane can be produced. The film forming method may be a known method such as a casting method using an applicator.
[ chemical 10]
2-2 Process for producing electrode Material
The conductive carrier and the catalyst are mixed in a predetermined amount by using a known mixer to prepare a carrier. The mixing time may be set to 3 to 60 minutes. Other methods for producing the support include a method in which the catalyst is deposited on the conductive support by a reduction reaction. More specifically, the catalyst metal can be supported on the conductive carrier by mixing predetermined amounts of the conductive carrier, the catalyst metal, and the reducing agent, and reducing the cations. The mixing time in this method may be set to 1 to 48 hours.
An organic solvent was charged into a container, and an anion exchange resin (ionomer) was charged into the container to dissolve the organic solvent, thereby preparing an ionomer solution. The ionomer concentration of the ionomer solution is 0.1 to 50 mass% with respect to the total amount of the ionomer solution, and the covering thickness and coverage can be adjusted by the ionomer concentration of the ionomer solution. The organic solvent used in the ionomer solution is not particularly limited as long as it can dissolve the ionomer, and the solubility of the ionomer may be selected from the group consisting of.
The obtained support is put into the ionomer solution to be produced, and mixed with a stirrer or the like to produce a support dispersion solution. The mixing time may be set to 5 to 60 minutes.
The obtained carrier dispersion solution is blown onto an electrode support such as carbon paper using a known blowing device such as a sprayer, and dried to prepare an electrode material attached to carbon paper or the like. The drying may be performed by natural drying, a drying oven as needed, or the like.
3. Use of electrode material
The electrode material of the present disclosure can be used for CO as an electrode, a membrane-electrode assembly, or the like 2 An electrolysis device.
3-1 membrane-electrode assembly
When the electrode material of the present disclosure is used to form a membrane-electrode assembly, CO can be obtained 2 A membrane-electrode assembly having high reduction efficiency.
The membrane-electrode assembly of the present disclosure includes the electrode material of the present disclosure, a solid electrolyte, and a current collector, and the electrode material of the present disclosure is used while being disposed between the solid electrolyte and the current collector. The electrode material may be formed into an electrode of a desired shape by molding or attaching the electrode material to a substrate. The solid electrolyte uses an anion exchange membrane.
3-1-1. Solid electrolyte
The solid electrolyte of the present disclosure is not particularly limited as long as the effect of the technology of the present disclosure is not hindered, and examples thereof include cation exchange membranes such as Nafion (registered trademark) and Aquivion (registered trademark); anion exchange membranes such as sustinion (registered trademark) and Fumasep (registered trademark) are preferably used. In the membrane-electrode assembly of the present disclosure, an anion exchange membrane obtained by mixing a plurality of such ion exchange groups with a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group is particularly preferably used. Specific examples of usable materials include a cover (registered trademark) and ASE, AHA, AMX, ACS, AFN, AFX (manufactured by the trunk corporation); seta (registered trademark), AMV, AMT, DSV, AAV, ASV, AHO, AHT, APS (manufactured by asahi corporation), and the like. Further, an ion exchange membrane obtained by forming an ionomer of the following formula (1) into a membrane or the like can be used.
[ chemical 11]
The anion exchange membrane may be made of the same material as or different from the anion exchange resin covering the electrode material of the present disclosure. In the case where the material of the anion exchange membrane is the same as the anion exchange resin covering the electrode material of the present disclosure, CO suppression can be provided 2 Membrane-electrode assembly and CO capable of stable operation with reduced reduction efficiency 2 An electrolysis device. In addition, when the anion exchange resin and the anion exchange membrane are combined, the following effects are also exhibited: the interface between the anion exchange resin and the anion exchange membrane can be prevented from being deteriorated, and the phase separation at the interface between the anion exchange resin and the anion exchange membrane can be prevented, thereby allowing smooth movement (conduction) of ions.
The ion exchange capacity of the anion exchange membrane is 0.3mmol/g or more and 3.5mmol/g or less, preferably 0.5mmol/g or more and 2.5mmol/g or less. In the case where the ion exchange capacity of the anion exchange membrane falls within this range, CO inhibition can be provided 2 Membrane-electrode assembly and CO, which have reduced reduction efficiency and can realize stable operation at lower voltage 2 An electrolysis device.
3-1-2. Collector
Examples of the current collector described in the present disclosure include metal materials such as copper (Cu), nickel (Ni), stainless steel (SUS), nickel-plated steel, and brass, and among these, copper is preferable from the viewpoints of ease of processing and cost. In the case where the current collector is a metal material, examples of the shape of the negative electrode current collector include a metal foil, a metal plate, a metal thin film, a metal expanded metal, a punched metal, and a foamed metal.
Here, the current collector is provided with a vent hole for supplying and recovering a gas (raw material gas, generated gas) to and from the electrode (or electrode material). By using these vent holes, the raw material gas (including unreacted raw material gas) can be fed uniformly and efficiently to the electrode (or electrode material) and generated. The number, position and size of the ventilation holes are not limited, and may be appropriately set. In addition, when the current collector has air permeability, no vent hole is required. Fig. 3 shows an explanatory view of the membrane-electrode assembly, but the current collector in fig. 3 shows a current collector using a porous material.
Examples
Next, the technology of the present disclosure will be described in detail with reference to examples and comparative examples, but the technology of the present disclosure is not limited to these.
Production of electrode Material
< Synthesis of anion exchange resin (ionomer) ]
The ionomer of the above formula (1) having different ion exchange capacities was synthesized as the ionomer of examples 1 and 2 by the above method.
< preparation of electrode >
Ag nanoparticles (particle size 1-100 nm) as catalyst were passed through Ag in an amount of 2mg and 10mg of conductive carbon black (average particle size 30 nm) by using a mixer (device name, process conditions) + The powder obtained by precipitation of the ions by reduction was mixed to prepare a carrier. The support was dispersed in an ionomer solution prepared by dissolving 6mg of an ionomer having a different ion exchange capacity in an organic solvent in a container, and the solution was applied to a carbon paper (area: 2.25 cm) using a sprayer 2 ) The electrodes of examples 1 and 2 were prepared. The same method was also used to produce the ionomer of comparative examples 1 to 2, and the electrode was used as the electrode of comparative examples 1 to 2. The coverage of the electrode materials of each example and comparative example was 100%.
(raw materials)
Ionomer of example 1: an ionomer of formula (1) having an ion exchange capacity of 2.1mmol/g
Ionomer of example 2: an ionomer of formula (1) having an ion exchange capacity of 1.5mmol/g
Ionomer of comparative example 1: ion exchange capacity of 2.0mmol/g, FAA-3-50 manufactured by FUMATECHHBWT GmbH Co
Ionomer of comparative example 2: the ion exchange capacity was 1.1mmol/g and XA-9 manufactured by Dioxide Materials Co
<CO 2 Electrolysis device>
The electrodes of each of the examples and comparative examples thus obtained were used as cathodes, and titanium mesh carrying iridium oxide was used as anodes. As the solid electrolyte, an anion exchange membrane having an ion exchange capacity of 1.5mmol/g and a membrane thickness of 30 to 35 μm was used. Respectively putting the electrolyte tank (0.5M KHCO) 3 Aqueous solution) was used as the solution on the anode side. The structure is formed by arranging a cathode, a solid electrolyte, an anode and an electrolyte tank in sequence, and the cathode and the electrolyte tank clamp an ion exchange membrane and the anode. Evaluation is carried out by 2 :N 2 The gas obtained by mixing at a volume ratio of =3:1 was supplied to the cathode, and the applied potential of the cathode was set at-1.8V with respect to the silver/silver chloride reference electrode.
< evaluation >
< evaluation of electrolytic Property >
CO using electrodes incorporated with each example and each comparative example 2 Electrolysis device for CO 2 Electrolysis was performed to measure the current density J of CO produced when CO was produced CO [mA/cm 2 ]。
TABLE 1
< evaluation of stability >
CO incorporating the electrode of example 1 2 The solid electrolyte of the electrolyzer was changed to the ion exchange membrane shown below as CO of examples A to D, respectively 2 The stability was evaluated by an electrolysis apparatus. In the stability evaluation, in the followingUnder the same conditions as the above electrolytic performance evaluation, the operation was continuously performed for 20 hours, and the operation was performed on CO 2 Electrolysis was performed to measure the current density J of CO produced when CO was produced CO [mA/cm 2 ]. The stability evaluation was performed according to the following evaluation criteria. The results are shown in Table 2.
(solid electrolyte)
Example a: an ionomer of formula (1) having an ion exchange capacity of 1.0mmol/g
Example B: an ionomer of formula (1) having an ion exchange capacity of 1.5mmol/g
Example C: an ionomer of formula (1) having an ion exchange capacity of 2.1mmol/g
Example D: FAS-30 made by FuMATECHHBWT GmbH with an ion exchange capacity of 1.8mmol/g
(evaluation criterion)
And (3) the following materials: j20 hours after initiation of electrolysis CO 50mA/cm 2 The CO selectivity after 20 hours from the start of electrolysis was 90% or more.
And (2) the following steps: j20 hours after initiation of electrolysis CO 50mA/cm 2 The CO selectivity after 20 hours from the start of electrolysis was less than 90%.
Delta: j20 hours after initiation of electrolysis CO Less than 50mA/cm 2 。
TABLE 2
Description of the reference numerals
1. Electrode material
10. Conductive carrier
11. Catalyst (active site)
12. Ion exchange resin
100 CO 2 Electrolysis device
101. Cathode (cathod)
101-1 cathode surface in contact with solid electrolyte
101-2 cathode surface in contact with collector
102. Anode (anode)
102-1 face of anode in contact with support plate
102-2 face of anode in contact with solid electrolyte
103. Solid electrolyte
104. Current collector
Gas supply hole of 104-1 current collector
Gas recovery hole of 104-2 current collector
105. Support plate
Gas flow passage of 105-1 support plate
106. Voltage applying part

Claims (6)

1.CO 2 An electrolysis device having an electrode material comprising a carrier and an anion exchange resin,
the carrier comprises a conductive carrier and a catalyst, the catalyst is carried on the conductive carrier and comprises any one or more of metal complex particles, metal particles or inorganic compound particles,
the anion exchange resin covers a part or the whole of the surface of the carrier and comprises an ionomer of the following formula (1),
[ chemical 1]
Wherein m and n represent natural numbers of 1 to 200.
2. The CO according to claim 1 2 The electrolytic device is characterized in that the ion exchange capacity of the anion exchange resin is more than 0.5mmol/g and less than 3.5mmol/g.
3. CO according to claim 1 or 2 2 An electrolytic device comprising a membrane-electrode assembly comprising the electrode materialA solid electrolyte and a current collector,
the electrode material is disposed between the solid electrolyte and the current collector.
4. A CO according to claim 3 2 The electrolysis apparatus is characterized in that the solid electrolyte is an anion exchange membrane.
5. The CO of claim 4 2 An electrolysis apparatus, characterized in that the anion exchange membrane comprises an ionomer of the following formula (1),
[ chemical 2]
Wherein m and n represent natural numbers of 1 to 200.
6. A CO according to claim 4 or 5 2 The electrolysis device is characterized in that the ion exchange capacity of the anion exchange membrane is more than 0.3mmol/g and less than 3.5mmol/g.
CN202280035394.7A 2021-05-19 2022-05-17 CO 2 Electrolysis device and CO 2 Method for producing electrolytic product Pending CN117355638A (en)

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