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WO2022118364A1 - Procédé de fabrication d'électrode de réduction portée sur film d'électrolyte - Google Patents

Procédé de fabrication d'électrode de réduction portée sur film d'électrolyte Download PDF

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Publication number
WO2022118364A1
WO2022118364A1 PCT/JP2020/044615 JP2020044615W WO2022118364A1 WO 2022118364 A1 WO2022118364 A1 WO 2022118364A1 JP 2020044615 W JP2020044615 W JP 2020044615W WO 2022118364 A1 WO2022118364 A1 WO 2022118364A1
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Prior art keywords
electrolyte membrane
electrode
carbon dioxide
reduction
reducing
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PCT/JP2020/044615
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English (en)
Japanese (ja)
Inventor
紗弓 里
裕也 渦巻
晃洋 鴻野
武志 小松
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Nippon Telegraph and Telephone Corp
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Nippon Telegraph and Telephone Corp
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Priority to PCT/JP2020/044615 priority Critical patent/WO2022118364A1/fr
Priority to JP2022566519A priority patent/JP7587167B2/ja
Publication of WO2022118364A1 publication Critical patent/WO2022118364A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • 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

Definitions

  • the present invention relates to a method for manufacturing an electrolyte membrane-supported reducing electrode.
  • Non-Patent Documents 1 to 3 a reduction device that reduces carbon dioxide
  • a reduction device that uses artificial photosynthesis technology that applies light energy such as sunlight to reduce carbon dioxide and an electrolytic decomposition device that reduces carbon dioxide by applying electrical energy from the outside.
  • FIG. 2 of Non-Patent Document 1 illustrates a carbon dioxide reducing device by light irradiation.
  • An electrolyte membrane is placed between the oxidation tank on the left side and the reduction tank on the right side, and the oxidation tank and the reduction tank are each filled with an aqueous solution.
  • An oxide electrode of gallium nitride (GaN) is placed in the oxide tank, a reduction electrode of copper (Cu) is placed in the reduction tank, and the oxide electrode and the reduction electrode are connected by a lead wire.
  • helium (He) flows into the aqueous solution in the oxidation tank, and carbon dioxide (CO 2 ) flows into the aqueous solution in the reduction tank.
  • He helium
  • CO 2 carbon dioxide
  • a carbon dioxide phase reduction device that fills the reduction tank with carbon dioxide in the gas phase in order to increase the supply of carbon dioxide to the reduction electrode.
  • a reducing electrode is directly formed on the electrolyte membrane based on the fact that protons cannot move in carbon dioxide in the gas phase.
  • the forming method there is a electroless plating method using a metal salt solution containing metal ions and a reducing agent solution for reducing metal ions.
  • a metal salt solution and a reducing agent solution are simultaneously injected into one side of the electrolyte membrane and the other side thereof.
  • the reducing agent of the reducing agent solution permeates the electrolyte membrane and comes into contact with the metal salt solution, the metal ions in the metal salt solution are reduced and the metal is deposited on one side of the electrolyte membrane.
  • the metal salt solution is a small amount but the electrolyte membrane is before the reducing agent of the reducing agent solution permeates the electrolyte membrane and comes into contact with the metal salt solution. It penetrates into the inside of. As a result, the reducing agent solution and the metal salt solution come into contact with each other inside the electrolyte membrane, and the reducing electrode is formed so as to sink into the electrolyte membrane.
  • carbon dioxide cannot be supplied to the reducing electrode formed inside the electrolyte membrane, and since the electrolyte membrane contains water in the membrane, the water in the electrolyte membrane reacts with the dissolved oxygen in the electrolyte membrane.
  • the reducing electrode is oxidized.
  • the reduction reaction of the oxidized reducing electrode itself proceeds preferentially.
  • the reduction reaction of carbon dioxide is suppressed, and the efficiency of the reduction reaction of carbon dioxide is lowered.
  • a carbon dioxide gas phase reduction device generally, an operation of repeatedly turning on and off light energy or electric energy is carried out by a solar ascending / descending cycle or a maintenance cycle.
  • the reducing electrode formed inside the electrolyte membrane oxidizes in a state where the energy is OFF, and when the energy is turned ON again, the reduction reaction of the oxidized reducing electrode proceeds preferentially, so that the reduction of carbon dioxide The efficiency of the reaction is reduced.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to form a reducing electrode inside an electrolyte membrane in an electrolyte membrane-supported reducing electrode constituting a gas phase reducing device for carbon dioxide. It is to provide a technique capable of suppressing this and improving the efficiency of the reduction reaction of carbon dioxide.
  • the method for producing an electrolyte membrane-supported reducing electrode is to obtain an electrolyte membrane-supported reducing electrode arranged between an oxide tank including an oxide electrode and a reduction tank in which carbon dioxide is supplied to the inside of the empty space.
  • a first step of immersing one side of the electrolyte membrane in a reducing agent solution and a second step of immersing one side of the electrolyte membrane in a metal salt solution containing metal ions are performed.
  • the electrolyte membrane-supported reducing electrode constituting the gas phase reducing device for carbon dioxide it is possible to suppress the formation of the reducing electrode inside the electrolyte membrane, and the efficiency of the carbon dioxide reduction reaction can be improved. Can provide improveable technology.
  • FIG. 1 is a diagram showing a manufacturing process of an electrolyte membrane-supported reducing electrode.
  • FIG. 2 is a diagram showing a reaction system of an electroless plating method.
  • FIG. 3 is a diagram showing an image of formation of a reducing electrode with respect to the electrolyte membrane.
  • FIG. 4 is a diagram showing a configuration example of the carbon dioxide gas phase reducing device according to the first embodiment.
  • FIG. 5 is a diagram showing an operation example of a carbon dioxide gas phase reducing device.
  • FIG. 6 is a diagram showing a configuration example of a carbon dioxide gas phase reducing device according to Example 6.
  • the present invention relates to a manufacturing method for manufacturing an electrolyte membrane-supported reducing electrode in which a reducing electrode is directly formed on an electrolyte membrane by a electroless plating method using a metal salt solution and a reducing agent solution.
  • the present invention is characterized in that one side of the electrolyte membrane is immersed in a reducing agent solution before the electroless plating treatment is performed on the electrolyte membrane.
  • the reducing agent solution diffuses and permeates to one side of the electrolyte film (the surface on which the reducing electrode is formed) before the electrolytic plating process. Electrodes can be formed. That is, since the formation of the reducing electrode inside the electrolyte membrane can be suppressed at the time of producing the reducing electrode and at the time of stopping the reduction reaction, the oxidation of the reducing electrode can be suppressed and the efficiency of the reduction reaction of carbon dioxide can be improved.
  • FIG. 1 is a diagram showing a manufacturing process of an electrolyte membrane-supported reducing electrode.
  • Nafion registered trademark
  • the metal salt solution and the reducing agent solution each solution prepared as shown in Table 1 is used.
  • the reducing agent solution a solution containing sodium borohydride (NaBH 4 ), which is a polar compound, as the main component of the reducing agent is used.
  • step 1 polishing paper is rubbed against one side of the electrolyte membrane to roughen the one side (S1).
  • step 2 the electrolyte membrane is immersed in boiling nitric acid for 60 minutes (S2), and in step 3, the electrolyte membrane is immersed in boiling pure water for 60 minutes (S3). ..
  • step 3 the electrolyte membrane is immersed in boiling pure water for 60 minutes (S3). ..
  • the electrolyte membrane 1 is arranged between the first tank 11 and the second tank 12. At this time, the roughened surface of the electrolyte membrane 1 is arranged toward the first tank 11.
  • step 4 the second tank 12 is filled with the reducing agent solution 22 and left for 1 minute, and the opposite surface (opposite surface of the roughened surface) of the electrolyte membrane 1 is covered with the reducing agent solution 22. Immerse in (S4).
  • step 5 the first tank 11 is filled with the metal salt solution 21 containing metal ions and left for 30 minutes, and the roughened surface of the electrolyte film 1 is immersed in the metal salt solution 21. (S5).
  • Step 5 is a step of arranging the metal salt solution 21 and the reducing agent solution 22 so as to be in contact with each other across the electrolyte membrane 1 and performing electrolytic plating treatment. That is, in step 5, the opposite surface of the electrolyte membrane 1 is immersed in the reducing agent solution 22, and the roughened surface of the electrolyte membrane is immersed in the metal salt solution 21. This is a step of precipitating metal for an electrode.
  • step 4 since sodium borohydride, which is the main component of the reducing agent solution 22, is a polar compound, it diffuses and permeates the inside of the electrolyte membrane 1.
  • step 5 a redox reaction (BH 4 ⁇ + 4OH ⁇ ⁇ BO 2 ⁇ + 2H 2 O + 2H 2 + 4e ⁇ , Cu 2 + + 2e ⁇ ⁇ Cu) occurs at the interface between the metal salt solution 21 and the electrolyte membrane 1 to generate copper. Precipitates.
  • the electrolyte membrane-supported reducing electrode 30 in which the reducing electrode 2 is directly formed on the initial surface of the electrolyte membrane 1 is obtained.
  • the electrolyte membrane for example, a solid polymer membrane that conducts a cation or an anion, or an electrolyte membrane having a skeleton made of carbon-fluorine, such as Nafion, Foreblue, or Aquivion (registered trademark) may be used.
  • any kind of metal such as Ni, Pt, Au, Ag, Pd, Sn, Pd may be formed, and the metal may be formed.
  • a metal complex may be formed by subjecting the metal to an oxidation reaction or a substitution reaction.
  • FIG. 4 is a diagram showing a configuration example of the carbon dioxide gas phase reducing device 100 according to the first embodiment.
  • the gas phase reduction device 100 is a reduction device (artificial photosynthesis device) that causes a reduction reaction of carbon dioxide at the reduction electrode by irradiating the oxidation electrode with light.
  • a gas phase reducing device 100 it is simply referred to as a gas phase reducing device 100.
  • the gas phase reduction device 100 includes an oxidation tank 41 and a reduction tank 44 formed by dividing the internal space of one housing into two.
  • the oxide tank 41 is filled with the aqueous solution 43, and the oxide electrode 42 made of a semiconductor or a metal complex is inserted into the aqueous solution 43.
  • the reduction tank 44 adjacent to the oxidation tank 41 is filled with carbon dioxide gas or a gas containing carbon dioxide in the empty space.
  • the oxide electrode 42 is a compound that exhibits photoactivity and redox activity, such as a nitride semiconductor, titanium oxide, amorphous silicon, a ruthenium complex, and a rhenium complex.
  • the aqueous solution 43 is, for example, a potassium hydrogen carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a potassium chloride aqueous solution, a sodium chloride aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a rubidium hydroxide aqueous solution, or a cesium hydroxide aqueous solution.
  • the electrolyte membrane-supported reducing electrode 30 manufactured by the above manufacturing method is arranged between the oxidation tank 41 and the reduction tank 44.
  • the electrolyte membrane 1 is arranged on the oxidation tank 41 side, and the reduction electrode 2 is arranged on the reduction tank 44 side.
  • the oxidation electrode 42 and the reduction electrode 2 are connected by a conducting wire 45.
  • a tube 46 is inserted into the oxidation tank 41 in order to allow helium to flow into the aqueous solution 43 in the oxidation tank 41. Since carbon dioxide flows into the reduction tank 44, a gas input port 47 is formed at the bottom of the reduction tank 44. Further, in order to operate the gas phase reduction device 100, the light source 48 is arranged to face the oxide electrode 42.
  • the light source 48 is, for example, a xenon lamp, a pseudo-solar light source, a halogen lamp, a mercury lamp, sunlight, or a combination thereof.
  • Electrochemical measurement and gas / liquid production amount measurement Electrochemical measurement and gas / liquid production amount measurement will be described.
  • the oxidation tank 41 is filled with the aqueous solution 43.
  • a thin film of gallium nitride (GaN), which is an n-type semiconductor, and a thin film of aluminum gallium nitride (AlGaN) are epitaxially grown on a sapphire substrate in this order, and nickel (Ni) is vacuum-deposited on the thin film.
  • a substrate on which a nickel oxide (NiO) co-catalyst thin film was formed was used by performing the heat treatment. Then, the oxidation electrode 42 was installed in the oxidation tank 41 so as to be immersed in the aqueous solution 43.
  • the aqueous solution 43 was a 1.0 mol / L potassium hydroxide aqueous solution.
  • the light source 48 a 300 W high-pressure xenon lamp (wavelength 450 nm or more cut, illuminance 6.6 mW / cm 2 ) is used, and the surface on which the oxidation assist catalyst of the semiconductor optical electrode of the oxide electrode 42 is formed (the surface on which NiO is formed). ) was fixed so as to be the irradiation surface.
  • the light irradiation area of the oxidation electrode 42 was set to 2.5 cm 2 .
  • Helium was poured into the oxidation tank 41 from the tube 46, and carbon dioxide was poured into the reduction tank 44 from the gas input port 47 at a flow rate of 5 ml / min and a pressure of 0.18 MPa, respectively.
  • the carbon dioxide reduction reaction can proceed at the three-phase interface composed of [electrolyte film-copper (reducing electrode) -gas phase carbon dioxide] in the electrolyte membrane-supported reducing electrode 30.
  • the oxidation electrode 42 was uniformly irradiated with light for 300 minutes using the light source 48. By irradiating the oxide electrode 42 with light, electrons flow between the oxide electrode 42 and the reduction electrode 2.
  • the current value between the oxide electrode 42 and the reduction electrode 2 at the time of light irradiation was measured with an electrochemical measuring device (1287 type potentiogalvanostat manufactured by Solartron).
  • the gas and liquid in the oxidation tank 41 and the reduction tank 44 were collected at an arbitrary time during light irradiation, and the reaction products were analyzed by a gas chromatograph, a liquid chromatograph, and a gas chromatograph mass spectrometer. As a result, it was confirmed that oxygen was generated in the oxide tank 41 and hydrogen, carbon monoxide, formic acid, methane, methanol, ethanol and ethylene were generated in the reduction tank 44.
  • Example 2 In Example 2, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 10 minutes. Other conditions are the same as in Example 1.
  • Example 3 In Example 3, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 30 minutes. Other conditions are the same as in Example 1.
  • Example 4 In Example 4, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 60 minutes. Other conditions are the same as in Example 1.
  • Example 5 In Example 5, as shown in FIG. 5, the operation of irradiating the oxide electrode 42 with light for 60 minutes (ON) and stopping for 30 minutes (OFF) is repeated, and the total light irradiation time to the oxide electrode 42 is performed. The measurement was stopped when the time reached 300 minutes. Other conditions are the same as in Example 3.
  • Example 6 Manufacturing method of electrolyte membrane-supported reducing electrode
  • the electrolyte membrane-supported reducing electrode 30 is manufactured by the same procedure as in Example 1.
  • FIG. 6 is a diagram showing the configuration of the carbon dioxide gas phase reducing device 100 according to the sixth embodiment.
  • the carbon dioxide gas phase reduction device 100 is an apparatus (electrolytic reduction reaction apparatus) for an electrolytic reduction reaction of carbon dioxide in the gas phase. Hereinafter, it is simply referred to as a gas phase reducing device 100.
  • the gas phase reduction device 100 includes an oxidation tank 41 and a reduction tank 44 formed by dividing the internal space of one housing into two.
  • the oxide tank 41 is filled with the aqueous solution 43, and the oxide electrode 42 made of a semiconductor or a metal complex is inserted into the aqueous solution 43.
  • the reduction tank 44 adjacent to the oxidation tank 41 is filled with carbon dioxide gas or a gas containing carbon dioxide in the empty space.
  • the oxide electrode 42 is, for example, platinum, gold, silver, copper, indium, or nickel. Specific examples of the aqueous solution 43 are the same as in Example 1.
  • the electrolyte membrane-supported reducing electrode 30 manufactured by the above manufacturing method is arranged between the oxidation tank 41 and the reduction tank 44.
  • the electrolyte membrane 1 is arranged on the oxidation tank 41 side, and the reduction electrode 2 is arranged on the reduction tank 44 side.
  • the oxidation electrode 42 and the reduction electrode 2 are connected by a conducting wire 45.
  • a tube 46 is inserted into the oxidation tank 41 in order to allow helium to flow into the aqueous solution 43 in the oxidation tank 41. Since carbon dioxide flows into the reduction tank 44, a gas input port 47 is formed at the bottom of the reduction tank 44. Further, in order to operate the gas phase reducing device 100, the power supply 49 is connected to the conducting wire 45.
  • Electrochemical measurement and gas / liquid production amount measurement Electrochemical measurement and gas / liquid production amount measurement will be described.
  • the oxidation tank 41 is filled with the aqueous solution 43.
  • Platinum manufactured by Niraco
  • the oxide electrode 42 was used for the oxide electrode 42.
  • About 0.55 cm 2 of the surface area of the oxidation electrode 42 was installed in the oxide tank 41 so as to be submerged in the aqueous solution 43.
  • the aqueous solution 43 was a 1.0 mol / L potassium hydroxide aqueous solution.
  • Helium was poured into the oxidation tank 41 from the tube 46, and carbon dioxide was poured into the reduction tank 44 from the gas input port 47 at a flow rate of 5 ml / min and a pressure of 0.18 MPa.
  • the carbon dioxide reduction reaction can proceed at the three-phase interface composed of [electrolyte film-copper (reducing electrode) -gas phase carbon dioxide] in the electrolyte membrane-supported reducing electrode 30.
  • the area of the reducing electrode 2 to which carbon dioxide is directly supplied is about 6.25 cm 2 .
  • the oxidation electrode 42 and the reduction electrode 2 are connected by a lead wire 45 via a power supply 49, and a voltage of 2.0 V is applied.
  • the electron was allowed to flow for 300 minutes.
  • the current value between the oxide electrode 42 and the reduction electrode 2 when a voltage of 2.0 V was applied was measured by an electrochemical measuring device.
  • the gas and liquid in the oxidation tank 41 and the reduction tank 44 were sampled at an arbitrary time while the voltage was applied, and the reaction products were analyzed by a gas chromatograph, a liquid chromatograph, and a gas chromatograph mass spectrometer. As a result, it was confirmed that oxygen was generated in the oxide tank 41 and hydrogen, carbon monoxide, formic acid, methane, methanol, ethanol and ethylene were generated in the reduction tank 44.
  • Example 7 In Example 7, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 10 minutes. Other conditions are the same as in Example 6.
  • Example 8 In Example 8, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 30 minutes. Other conditions are the same as in Example 6.
  • Example 9 In Example 9, in step 4 of the method for manufacturing the electrolyte membrane-supported reducing electrode 30, the immersion time of the electrolyte membrane 1 in the reducing agent solution 22 was set to 60 minutes. Other conditions are the same as in Example 6.
  • Example 10 In Example 10, as shown in FIG. 5, the operation of applying the voltage by the power supply 49 for 60 minutes (ON) and stopping for 30 minutes (OFF) was repeated, and the total voltage application time became 300 minutes. When I stopped the measurement. Other conditions are the same as in Example 8.
  • [Comparison target example 1] Manufacturing method of electrolyte membrane-supported reducing electrode]
  • the metal salt solution 21 and the reducing agent solution 22 are placed in the first tank 11 without performing step 4 (immersion of the electrolyte membrane 1 in the reducing agent solution 22).
  • the second tank 12 were injected at the same time.
  • Other manufacturing methods are the same as in Example 1.
  • the reducing electrode 2 is inside the electrolyte membrane 1 from the roughened surface of the electrolyte membrane 1 to a depth of 300 nm. It was formed to immerse itself in.
  • Table 2 shows the Faraday efficiency of carbon dioxide reduction according to Examples 1 to 4, 6 to 9 and Comparative Examples 1 and 3.
  • Table 2 shows the Faraday efficiency (integrated value) of carbon dioxide reduction when light irradiation or voltage is continuously applied for 300 minutes.
  • Table 3 shows the Faraday efficiency of carbon dioxide reduction according to Examples 5 and 10 and Comparative Examples 2 and 4.
  • Table 3 shows the Faraday efficiency (integrated value) of carbon dioxide reduction after 300 minutes when the operation of turning on the light irradiation or applying the voltage for 60 minutes and turning off the voltage for 30 minutes is repeated.
  • the Faraday efficiency of carbon dioxide reduction indicates the ratio of the number of electrons used in the carbon dioxide reduction reaction to the number of electrons flowing between the electrodes by light irradiation or voltage application. The value.
  • the "number of electrons in the reduction reaction of carbon dioxide" in the formula (3) can be obtained by converting the measured value of the integrated production amount of the reduction product of carbon dioxide into the number of electrons required for the production reaction.
  • the concentration of the reduction reaction product is A [ppm]
  • the flow rate of the carrier gas is B [L / sec]
  • the number of electrons required for the reduction reaction is Z [mol]
  • the Faraday constant is F [C / mol]
  • the molar of the gas It was calculated using the formula (4) when the body was Vm [L / mol] and the light irradiation time or the voltage application time was T [sec].
  • Electron value of carbon dioxide reduction reaction [C] (A ⁇ B ⁇ Z ⁇ F ⁇ T ⁇ 10-6 ) / Vm ⁇ ⁇ ⁇ (4) From Table 2, it was confirmed that in Examples 1 to 4 and Examples 6 to 9, the Faraday efficiency of carbon dioxide reduction was improved as compared with Comparative Example 1 and Comparative Example 3, respectively. It is considered that this is because in each of Examples 1 to 4 and 6 to 9, the reducing electrode did not sink into the inside of the electrolyte membrane, and the reducing electrode could be formed from directly above the electrolyte membrane.
  • Example 1 to 10 unlike the comparative examples 1 to 4, the electrolyte membrane was immersed in the reducing agent solution as step 4 before the electroless plating treatment. As a result, the reducing agent solution diffused and permeated to the roughened surface of the electrolyte film before the electrolytic plating treatment, so that when the metal salt solution was injected into the first tank, the reducing electrode was released from directly above the roughened surface of the electrolyte film. It is formed.
  • Comparative Examples 1 to 4 the metal salt solution and the reducing agent solution were simultaneously injected into the first tank and the second tank without performing step 4. In this case, only a small amount of the metal salt solution permeates the inside of the electrolyte membrane. Therefore, before the reducing agent solution penetrates to the roughened surface of the electrolyte membrane, the metal salt solution comes into contact with the inside of the electrolyte membrane, and the reducing electrode is formed so as to sink into the electrolyte membrane. Further, in the cases of Comparative Target Examples 1 to 4, carbon dioxide cannot be supplied to the portion of the reducing electrode formed inside the electrolyte membrane, and the electrolyte membrane contains water in the membrane, so that the electrolyte is used. The water in the membrane reacts with the dissolved oxygen in the electrolyte membrane to oxidize the reducing electrode. As a result, the reduction reaction of the oxidized electrode itself proceeds preferentially, and the carbon dioxide reduction reaction is suppressed.
  • step 4 in Examples 1 to 10 the reduction electrode was suppressed from being embedded in the electrolyte membrane, and the efficiency of the carbon dioxide reduction reaction was improved.
  • Example 1 to 4 and Examples 6 to 9 Comparing the Faraday efficiencies of carbon dioxide reduction in Examples 1 to 4 and Examples 6 to 9, the immersion time of the electrolyte membrane in the reducing agent solution in step 4 is 30 minutes or more in Examples 3 and 4. And Examples 8 and 9 are higher than Examples 1 and 2 and Examples 6 and 7 which are less than 30 minutes. Analyzing the depth of the reducing electrode sunk into the electrolyte membrane with respect to the immersion time, it was found that each of Example 1 and Example 6, Example 2 and Example 7, Example 3 and Example 8, and Example 4 and Example 9 was obtained. , 250 nm, 150 nm, 20 nm, 20 nm.
  • the depth of the reducing electrode to be sunk becomes deep in the range of the immersion time of less than 30 minutes, and the saturation value is obtained at the depth of 20 nm in the immersion time of 30 minutes or more, and the Faraday efficiency of carbon dioxide reduction is obtained. Is expected to improve further. Therefore, it is desirable to immerse the electrolyte membrane in the reducing agent solution for 30 minutes or more in advance.
  • the reduction electrode can be suppressed from being embedded in the electrolyte membrane, and the reduction electrode can be suppressed from being oxidized in the OFF state. Therefore, the reduction reaction of carbon dioxide can be suppressed. Efficiency has improved.
  • the electrolyte membrane in the production of the electrolyte membrane-supported reducing electrode for gas phase reduction of carbon dioxide by the electroless plating method, the electrolyte membrane is immersed in the reducing agent solution before the electroless plating treatment, so that the reducing electrode is used. It is possible to suppress the formation of a reducing electrode inside the electrolyte membrane during production and when the reduction reaction is stopped. As a result, the oxidation of the reducing electrode can be suppressed, and the efficiency of the carbon dioxide reduction reaction can be improved.
  • Electrolyte film 2 Reduction electrode 11: First tank 12: Second tank 21: Metal salt solution 22: Reducing agent solution 30: Electrolyte film-supported reducing electrode 41: Oxidation tank 42: Oxidation electrode 43: Aqueous solution 44 : Reduction tank 45: Lead wire 46: Tube 47: Gas input port 48: Light source 49: Power supply

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Abstract

Procédé de fabrication d'une électrode de réduction portée sur un film d'électrolyte et disposée entre un réservoir d'oxydation, contenant une électrode d'oxydation, et un réservoir de réduction, comportant un vide intérieur alimenté en dioxyde de carbone, le procédé comprenant une première étape (S4) consistant à immerger la surface opposée à une première surface du film d'électrolyte dans une solution d'agent de réduction, et une seconde étape consistant à immerger la première surface du film d'électrolyte dans une solution de sel métallique contenant des ions métalliques.
PCT/JP2020/044615 2020-12-01 2020-12-01 Procédé de fabrication d'électrode de réduction portée sur film d'électrolyte Ceased WO2022118364A1 (fr)

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PCT/JP2020/044615 WO2022118364A1 (fr) 2020-12-01 2020-12-01 Procédé de fabrication d'électrode de réduction portée sur film d'électrolyte
JP2022566519A JP7587167B2 (ja) 2020-12-01 2020-12-01 電解質膜支持型還元電極の製造方法

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Citations (7)

* Cited by examiner, † Cited by third party
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JPS425014B1 (fr) * 1962-09-20 1967-03-01
JPS5636873B2 (fr) * 1978-09-07 1981-08-27
JPS58185790A (ja) * 1982-04-20 1983-10-29 Hitachi Zosen Corp イオン交換膜における電極の形成方法
JP2004197215A (ja) * 2002-08-23 2004-07-15 Eamex Co メッキによる電極形成方法、積層体及びこの積層体を用いた装置
JP2008223118A (ja) * 2007-03-15 2008-09-25 Mitsubishi Electric Corp 固体高分子電解質膜、その製造方法、および電気分解素子
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