WO2024116235A1 - Appareil de réduction de phase gazeuse pour dioxyde de carbone - Google Patents

Appareil de réduction de phase gazeuse pour dioxyde de carbone Download PDF

Info

Publication number
WO2024116235A1
WO2024116235A1 PCT/JP2022/043751 JP2022043751W WO2024116235A1 WO 2024116235 A1 WO2024116235 A1 WO 2024116235A1 JP 2022043751 W JP2022043751 W JP 2022043751W WO 2024116235 A1 WO2024116235 A1 WO 2024116235A1
Authority
WO
WIPO (PCT)
Prior art keywords
reduction
electrode
carbon dioxide
oxidation
concentration
Prior art date
Application number
PCT/JP2022/043751
Other languages
English (en)
Japanese (ja)
Inventor
紗弓 里
裕也 渦巻
晃洋 鴻野
浩伸 蓑輪
淳 荒武
Original Assignee
日本電信電話株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電信電話株式会社 filed Critical 日本電信電話株式会社
Priority to PCT/JP2022/043751 priority Critical patent/WO2024116235A1/fr
Publication of WO2024116235A1 publication Critical patent/WO2024116235A1/fr

Links

Images

Classifications

    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • 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
    • C25B3/26—Reduction of carbon dioxide

Definitions

  • This disclosure relates to a gas-phase carbon dioxide reduction device.
  • the technology of promoting the oxidation of water and the reduction of carbon dioxide by irradiating an oxidation electrode made of a photocatalyst with light is called artificial photosynthesis.
  • the technology of promoting the oxidation of water and the reduction of carbon dioxide by applying a voltage between an oxidation electrode and a reduction electrode made of metal is called electrolytic reduction of carbon dioxide.
  • Artificial photosynthesis technology that uses sunlight and electrolytic reduction technology that uses electricity derived from renewable energy sources can recycle carbon dioxide into carbon monoxide, formic acid, hydrocarbons such as ethylene, and alcohols such as methanol and ethanol.
  • Non-Patent Documents 1 and 2 artificial photosynthesis technology and carbon dioxide electrolytic reduction technology have used a reaction system in which a reduction electrode is immersed in an aqueous solution and carbon dioxide dissolved in the aqueous solution is supplied to the reduction electrode for reduction.
  • this carbon dioxide reduction method there are limitations to the concentration of carbon dioxide dissolved in the aqueous solution and the diffusion coefficient of carbon dioxide in the aqueous solution, which limits the amount of carbon dioxide supplied to the reduction electrode.
  • Non-Patent Document 3 by using a reaction device with a structure that can supply gas-phase carbon dioxide to the reduction electrode, the amount of carbon dioxide supplied to the reduction electrode is increased, and the reduction reaction of carbon dioxide is promoted.
  • the water oxidation reaction shown in formula (1) proceeds in the oxidation tank.
  • the carbon dioxide reduction reactions shown in formulas (2) to (5) proceed in combination with the water oxidation reaction on the oxidation tank side.
  • the reduction reaction of carbon dioxide proceeds by directly supplying gas-phase carbon dioxide to the interface between the electrolyte and the reduction electrode.
  • the reduction reaction can be started with carbon dioxide adsorbed at a high concentration at the interface in the early stages of the reaction, allowing the carbon dioxide reduction reaction to proceed with high efficiency.
  • the present disclosure has been made in consideration of the above circumstances, and an object of the present disclosure is to provide a technique capable of improving the efficiency of the reduction reaction of carbon dioxide in a gas-phase reduction device of carbon dioxide.
  • the gas-phase carbon dioxide reduction device reduces gas-phase carbon dioxide, and includes an oxidation tank including an oxidation electrode and a reference electrode, a reduction tank to which carbon dioxide is supplied, a composite disposed between the oxidation tank and the reduction tank, in which an electrolyte membrane and a reduction electrode are joined to each other, the electrolyte membrane is disposed on the oxidation tank side, and the reduction electrode is disposed on the reduction tank side, and a switch that connects the reduction electrode to the oxidation electrode or the reference electrode, and the switch is controlled by a control device or a user to connect the reduction electrode to the oxidation electrode, to connect the reduction electrode to the reference electrode when the rate of decrease in the concentration of a product generated by the reduction reaction of carbon dioxide at the reduction electrode exceeds a first threshold, and to connect the reduction electrode to the oxidation electrode when the change in the potential difference between the reduction electrode and the reference electrode falls below a second threshold.
  • This disclosure provides technology that can improve the efficiency of the carbon dioxide reduction reaction in a gas-phase carbon dioxide reduction device.
  • FIG. 1 is a diagram showing the overall configuration of a system according to a first embodiment.
  • FIG. 2 is a flow chart showing a method of operating the gas phase reduction device for carbon dioxide.
  • FIG. 3 is a diagram showing the overall configuration of a system according to the second embodiment.
  • FIG. 4 is a configuration diagram showing the overall configuration of a system according to a first comparative example.
  • FIG. 5 is a configuration diagram showing the overall configuration of a system according to the second comparative example.
  • FIG. 6 is a graph showing the change over time in the Faraday efficiency of the reduction reaction of carbon dioxide in Examples 1 and 2 and Comparative Examples 1 and 2.
  • the gas-phase carbon dioxide reduction device stops the carbon dioxide reduction reaction when the efficiency of the carbon dioxide reduction reaction has decreased by a certain amount, provides a time (standby time) for saturating the reaction field with carbon dioxide, and then restarts the carbon dioxide reduction reaction after the carbon dioxide is saturated.
  • the light energy or electrical energy provided during the redox reaction can be used efficiently for a long period of time in the carbon dioxide reduction reaction, without wasting it in the side reactions shown in formula (6).
  • the energy not consumed in the redox reaction during standby time can be stored or used for other purposes, making it possible to make effective use of energy.
  • Example 1 is a configuration diagram showing an overall configuration of a system 1 according to Example 1.
  • the system 1 includes a gas-phase carbon dioxide reduction device 10, a concentration measurement device 20, an electrochemical measurement device 30, and a control device 40.
  • the gas-phase carbon dioxide reduction device 10 is a device that performs artificial photosynthesis as described in the Background Art section. Specifically, the gas-phase carbon dioxide reduction device 10 is a device that irradiates light onto an oxidation electrode in an oxidation tank and performs a reduction reaction of gas-phase carbon dioxide at a reduction electrode in the reduction tank.
  • the gas-phase carbon dioxide reduction device 10 includes an oxidation tank 101 and a reduction tank 102 formed by dividing the internal space of a single housing in two.
  • the oxidation tank 101 is filled with a specific aqueous solution 103.
  • An oxidation electrode 104 is inserted into the aqueous solution 103.
  • Carbon dioxide or a gas containing carbon dioxide is supplied to the reduction tank 102 adjacent to the oxidation tank 101.
  • a reduction electrode/electrolyte membrane composite (composite) 105 in which an electrolyte membrane 105a and a reduction electrode 105b are in contact (joined) with each other, is disposed between the oxidation tank 101 and the reduction tank 102.
  • the electrolyte membrane 105a is disposed on the oxidation tank 101 side.
  • the reduction electrode 105b is disposed on the reduction tank 102 side.
  • the oxidation electrode 104 and the reduction electrode 105b are connected by a wire via the switch 106.
  • a reference electrode 107 is also inserted into the aqueous solution 103 in the oxidation tank 101.
  • the reference electrode 107 and the reduction electrode 105b are connected by a wire via the switch 106 and a voltmeter 108.
  • the switch 106 connects the reduction electrode 105b to the oxidation electrode 104 or the reference electrode 107.
  • the voltmeter 108 is also connected to the control device 40, as the control device 40 controls the switch 106 using the potential difference measured by the voltmeter 108.
  • a light source 109 is disposed opposite the oxidation electrode 104.
  • the aqueous solution 103 is, for example, an aqueous solution of potassium bicarbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of potassium chloride, an aqueous solution of sodium chloride, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of rubidium hydroxide, or an aqueous solution of cesium hydroxide.
  • the oxidized electrode 104 is, for example, a nitride semiconductor, titanium oxide, or amorphous silicon.
  • the oxidized electrode 104 may be a compound that exhibits photoactivity or redox activity, such as a ruthenium complex or a rhenium complex.
  • the electrolyte membrane 105a is, for example, Nafion (registered trademark), Forblue, or Aquivion, which are electrolyte membranes having a carbon-fluorine skeleton.
  • the electrolyte membrane 105a may also be Selemion or Neocepta, which are electrolyte membranes having a hydrocarbon skeleton.
  • the reduction electrode 105b is, for example, copper, platinum, gold, silver, indium, palladium, gallium, nickel, tin, or cadmium.
  • the reduction electrode 105b may be a porous body of an alloy of these.
  • the reduction electrode 105b may be a porous body of silver oxide, copper oxide, copper(II) oxide, nickel oxide, indium oxide, tin oxide, tungsten oxide, tungsten(VI) oxide, copper oxide, or the like.
  • the reduction electrode 105b may be a porous metal complex having a metal ion and an anionic ligand.
  • the switch 106 is, for example, a switch circuit that switches the connection destination to be selectable, or an on-off circuit that turns the electrical or physical connection state on and off.
  • the switch 106 may be controlled by the control device 40 or by the user.
  • the switch 106 may be built into the control device 40.
  • the reference electrode 107 is, for example, a silver-silver chloride electrode, a silver-silver ion electrode, a standard hydrogen electrode, a reversible hydrogen electrode, a calomel electrode, a mercury-mercury oxide electrode, or a mercury-mercury sulfide electrode.
  • the light source 109 is, for example, a xenon lamp, a pseudo-sun light source, a halogen lamp, a mercury lamp, or sunlight.
  • the light source 109 may be a combination of these.
  • the concentration measuring device 20 is connected to a gas output port 112 formed in the upper part of the reduction tank 102 by a gas pipe (not shown).
  • the concentration measuring device 20 is a device that measures the concentration of a product generated by a reduction reaction in the reduction tank 102.
  • the concentration measuring device 20 is, for example, a gas chromatograph, a gas chromatograph mass spectrometer, a liquid chromatograph, a semiconductor gas concentration sensor, or a gas concentration detector tube using a chemical reaction.
  • the concentration measuring device 20 may be configured by combining these.
  • the electrochemical measurement device 30 is connected to a conductor that is connected to the oxidation electrode 104.
  • the electrochemical measurement device 30 measures a current value during the reduction reaction (while the connection destination of the switch 106 is connected to the connection end T1 on the oxidation electrode side). The measured current value is used to calculate the Faraday efficiency of the reduction reaction and as a current value described later in "Modification 2 of Example 1".
  • the control device 40 is a device that controls the switch 106 based on the concentration of the product measured by the concentration measuring device 20 and the current value measured by the electrochemical measurement device 30.
  • the control device 40 is, for example, a computer device equipped with a CPU and a memory.
  • Example 1 (Method of Producing Reduction Electrode/Electrolyte Membrane Composite 105) Next, a method for producing the reduction electrode/electrolyte membrane composite 105 will be described.
  • a metal porous body having a thickness of 0.2 mm and a porosity of 80% was used as the reduction electrode 105b.
  • Nafion which is a cation exchange membrane, was used as the electrolyte membrane 105a.
  • Nafion was layered on top of the metal porous body and placed between two copper plates. This sample was then placed between a thermocompression device (hot press) and left for three minutes with a constant pressure applied vertically to the porous electrode surface of the metal porous body at a heating temperature of 150°C. The sample was then quickly cooled and removed from the thermocompression device to obtain a reduction electrode/electrolyte membrane composite 105.
  • the oxidation tank 101 is filled with a specific aqueous solution 103.
  • a 1.0 mol/L aqueous solution of potassium hydroxide is used as the aqueous solution 103.
  • the substrate thus formed was used as the oxidation electrode 104, and the oxidation electrode 104 was placed in the oxidation tank 101 so that it was immersed in the aqueous solution 103.
  • a 300 W high-pressure xenon lamp (cutting wavelengths of 450 nm or more, illuminance 2.2 mW/cm 2 ) was used as the light source 109.
  • the light source 109 was fixed so that the surface of the oxidation electrode 104 on which the oxidation promoter was formed was the irradiated surface.
  • the light irradiated area of the oxidation electrode 104 was 2.3 cm 2 .
  • Nitrogen (N) was flowed through the tube 110 into the aqueous solution 103 in the oxidation tank 101 at a flow rate of 30 ml/min.
  • Carbon dioxide (CO 2 ) was also flowed through the gas inlet 111 into the reduction tank 102 at the same flow rate. Then, the oxidation tank 101 was sufficiently replaced with nitrogen for 15 hours or more, and the reduction tank 102 was sufficiently replaced with carbon dioxide for the same period or more, after which light was uniformly irradiated from the light source 109 onto the oxidation electrode 104.
  • the switch 106 is controlled according to the flowchart shown in FIG. 2.
  • the control device 40 controls the switch 106.
  • Step S1 The control device 40 selects the connection terminal T1 on the oxidation electrode side as the connection destination of the switch 106, and connects the oxidation electrode 104 and the reduction electrode 105b. This causes the reduction reaction of carbon dioxide to proceed in the reduction electrode 105b.
  • Step S2 Next, the concentration of the product generated by the reduction reaction of carbon dioxide is measured by the concentration measuring device 20.
  • a gas chromatograph was used as the concentration measuring device 20, and the concentration of the product was measured every 30 minutes, and only carbon monoxide (CO) was detected as the product.
  • CO carbon monoxide
  • the current value between the oxidation electrode 104 and the reduction electrode 105b was measured by the electrochemical measurement device 30.
  • Step S3 Next, the control device 40 calculates the rate of decrease in the concentration of the product (CO concentration) being measured/detected, and determines whether or not the rate of decrease in the concentration has exceeded a first threshold value X.
  • the first threshold value X is the rate of decrease (%) of the concentration at which the concentration of the product can be considered to have started to decrease/fall. Specific examples will be described below.
  • the rate of decrease of the CO concentration from the initial value was calculated by the formula (7).
  • Q 0 is the initial value of the CO concentration.
  • Q is the CO concentration at an arbitrary time.
  • Decrease rate of CO concentration from initial value (Q 0 ⁇ Q ) ⁇ 100/Q 0 (7)
  • the slope of the change in concentration over time, E Q was used to determine whether the CO concentration had started to decrease or decline.
  • E Q was calculated from equation (8) using Q t as the CO concentration at any time t and Q t+ ⁇ t as the CO concentration at time (t+ ⁇ t).
  • the first threshold value X was determined to be 10 (%) as a value at which this EQ can be detected.
  • the method of determining the first threshold value X is not limited to the above method.
  • the first threshold value X may be any value that can detect a decrease or decline in the CO concentration.
  • the first threshold value X may be determined based on the amount of change from the average CO concentration, by fitting the change in the CO concentration over time, or based on the user's experience.
  • step S2 If the rate of decrease in density does not exceed the first threshold value X, the process returns to step S2.
  • Step S4 Next, when the rate of decrease in the concentration of the product (CO concentration) being measured/detected exceeds the first threshold value X, the control device 40 cuts off the connection to the connection terminal T1 on the oxidation electrode side of the switch 106 at that point, selects the connection terminal T2 on the reference electrode side, and connects the reduction electrode 105 b to the reference electrode 107.
  • the reaction field will be saturated with carbon dioxide, and the chemical potential of the electrode will change. Therefore, from this point on, this change will be measured as the potential difference from the reference electrode 107. As the reaction field becomes saturated with carbon dioxide, the potential difference will become smaller, and this point will be utilized.
  • Step S5 Next, the potential difference between the reference electrode 107 and the reduction electrode 105b is measured by a voltmeter 108.
  • the reference electrode 107 is a silver-silver chloride electrode.
  • Step S6 Next, the control device 40 calculates the amount of change in the potential difference between the reference electrode 107 and the reduction electrode 105b, and determines whether or not the amount of change in the potential difference has fallen below a second threshold value Y.
  • the second threshold value Y is the amount of change in the potential difference (V) at which the potential difference between the reference electrode 107 and the reduction electrode 105b can be considered to be stable. Specific examples will be described below.
  • Example 1 the stability of the absolute value
  • FV was calculated from formula (9) by assuming that the potential difference at any time t is Vt and the potential difference at time (t+ ⁇ t) is Vt + ⁇ t .
  • the method of determining the second threshold value Y is not limited to the above method.
  • the second threshold value Y may be any value that can detect that the amount of change in the potential difference has stabilized.
  • the second threshold value Y may be determined by fitting the change in the voltage value over time, or based on the user's experience.
  • step S6 if the result of the judgment in step S6 is that the change in the potential difference between the reference electrode 107 and the reduction electrode 105b is below the second threshold Y, the process returns to step S1.
  • step S1 the control device 40 at that point in time cuts off the connection to the connection end T2 on the reference electrode side of the switch 106, selects the connection end T1 on the oxidation electrode side, and connects the oxidation electrode 104 and the reduction electrode 105b. This causes the reduction reaction of carbon dioxide to proceed again.
  • the change in the potential difference is not below the second threshold Y, the process returns to step S5.
  • the switch 106 may be operated by a person who visually checks the product concentration and voltage value and makes the switching decision, or the concentration and voltage value may be automatically transmitted to a computer and automatic control may be performed using a control circuit or control device.
  • Example 2 (Modification 2 of Example 1)
  • the current value was not used, and the product concentration reduction rate was simply used.
  • the electrochemical measurement device 30 and the control device 40 are connected to each other, and the control device 40 executes a calculation process of dividing the product concentration measured by the concentration measurement device 20 by the current value measured by the electrochemical measurement device 30.
  • Example 2 is a diagram showing the overall configuration of a system 1 according to a second embodiment.
  • the system 1 has the same configuration as that of the first embodiment.
  • the gas-phase carbon dioxide reduction device 10 is the carbon dioxide electrolytic reduction device described in the Background Art section. Specifically, the gas-phase carbon dioxide reduction device 10 is a device that applies a voltage between an oxidation electrode and a reduction electrode, and performs a reduction reaction of gas-phase carbon dioxide at the reduction electrode in a reduction tank.
  • the carbon dioxide gas-phase reduction device 10 includes a power source 113 connected between the oxidation electrode 104 and the reduction electrode 105b as shown in FIG. 3, instead of the light source 109 shown in FIG. 1.
  • the oxidation electrode 104 according to the second embodiment is, for example, platinum, gold, silver, copper, indium, nickel, zinc, tin, or lead.
  • the oxidation electrode 104 may be an oxide of these metals.
  • the rest of the configuration is the same as that of the first embodiment.
  • the oxidation tank 101 is filled with a predetermined aqueous solution 103.
  • a 1.0 mol/L aqueous solution of potassium hydroxide is used as the aqueous solution 103.
  • the oxidation electrode 104 is placed in the oxidation tank 101 so that about 0.4 cm2 of its surface area is submerged in the aqueous solution 103.
  • the oxidation electrode 104 is made of platinum.
  • Helium He was flowed through the tube 110 into the aqueous solution 103 in the oxidation tank 101 at a flow rate of 30 ml/min.
  • Carbon dioxide (CO 2 ) was also flowed through the gas inlet 111 into the reduction tank 102 at the same flow rate.
  • the oxidation tank 101 was then thoroughly replaced with helium for 15 hours or more, and the reduction tank 102 was thoroughly replaced with carbon dioxide for the same period or more.
  • the switch 106 is controlled according to the flowchart shown in FIG. 2.
  • the specific control method is the same as in Example 1. A simple explanation will be given here.
  • the switch 106 is connected to the connection end T1 on the oxidation electrode side to connect the oxidation electrode 104 and the reduction electrode 105b. Then, the power supply 113 is operated at a constant current of 3.0 mA to allow the reduction reaction of carbon dioxide to proceed at the reduction electrode 105b.
  • the concentration of the product in the reduction tank 102 was measured every 30 minutes by the concentration measuring device 20. In Example 2, a gas chromatograph was also used as the concentration measuring device 20, and only carbon monoxide (CO) was detected as a product.
  • connection end T1 of the switch 106 on the oxidation electrode side is turned off and connected to the connection end T2 on the reference electrode side, connecting the reference electrode 107 and the reduction electrode 105b.
  • the potential difference between the reference electrode 107 and the reduction electrode 105b is then measured by the voltmeter 108.
  • a silver-silver chloride electrode was used for the reference electrode 107.
  • the rate of decrease from the initial value of the CO concentration was calculated by the above formula (7). From the time change of the CO concentration measured in advance, the EQ when the CO concentration was deemed to have turned to a decreasing trend was -290 (ppm/h). For this reason, in Example 2, the first threshold value X was determined to be 10 (%) as a value at which this EQ can be detected.
  • connection end T2 of the switch 106 on the reference electrode side is turned off and connected to the connection end T1 on the oxidation electrode side, connecting the oxidation electrode 104 and the reference electrode 107.
  • the second threshold Y was set to 0.01 (V) for the same reasons as in Example 1.
  • Comparative Example 1 For comparison with Example 1, the gas-phase carbon dioxide reduction device 10 shown in Fig. 4 was used. Comparative Example 1 differs from Example 1 shown in Fig. 1 in that it does not have the switch 106, the reference electrode 107, or the voltmeter 108. Also, the oxidation electrode 104 and the reduction electrode 105b are connected by a conductor. The rest of the configuration is the same as in Example 1. The gas-phase carbon dioxide reduction device 10 according to Comparative Example 1 was operated to continuously carry out the oxidation-reduction reaction, and was stopped when the total reaction time reached 100 hours.
  • Comparative Example 2 For comparison with Example 2, the gas-phase carbon dioxide reduction device 10 shown in Fig. 5 was used. Unlike Example 2 shown in Fig. 3, Comparative Example 2 does not have the switch 106, the reference electrode 107, or the voltmeter 108. In addition, the oxidation electrode 104 and the reduction electrode 105b are connected by a conductor via the power source 113. The rest of the configuration is the same as that of Example 2. The gas-phase carbon dioxide reduction device 10 according to Comparative Example 2 was operated to continuously carry out the oxidation-reduction reaction, and was stopped when the total reaction time reached 20 hours.
  • [Effects of Examples 1 and 2] 6 is a diagram showing the change over time in the Faraday efficiency of the reduction reaction of carbon dioxide in Examples 1 and 2 and Comparative Examples 1 and 2.
  • the Faraday efficiency as shown in formula (10), indicates the ratio of the total charge amount used in the reduction reaction to the total charge amount flowing between the oxidation electrode 104 and the reduction electrode 105b during light irradiation or application of a power supply voltage.
  • the “total charge consumed in the reduction reaction” (C) can be calculated by converting the measured amount of reduction product produced into the number of electrons required for the production reaction. It was calculated using formula (11) where A (ppm) is the concentration of the reduction reaction product, B (L/sec) is the flow rate of the carrier gas, Z (mol) is the number of electrons required for the reduction reaction, F (C/mol) is the Faraday constant, V m (L/mol) is the molar mass of gas, and t (sec) is the reaction time.
  • Total charge consumed in reduction reaction (A ⁇ B ⁇ Z ⁇ F ⁇ t ⁇ 10 ⁇ 6 )/V m (11)
  • a higher faradaic efficiency of the carbon dioxide reduction reaction indicates that the electrons flowing between the oxidation electrode 104 and the reduction electrode 105b can be efficiently consumed in the carbon dioxide reduction reaction.
  • Examples 1 and 2 have a higher Faraday efficiency for carbon dioxide reduction than Comparative Examples 1 and 2. This is thought to be because, in Comparative Examples 1 and 2, the amount of carbon dioxide in the reaction field gradually decreased as the reaction started, whereas in Examples 1 and 2, a waiting time was provided to saturate the carbon dioxide at the point when the efficiency fell below a threshold, so that carbon dioxide could always be sufficiently adsorbed in the reaction field and operation could be performed while maintaining a high Faraday efficiency. As a result, the applied light energy and electrical energy can be used efficiently for a long period of time in the carbon dioxide reduction reaction without being wasted on side reactions.
  • the switch 106 in Examples 1 and 2 connects the reduction electrode 105b to the oxidation electrode 104, connects the reduction electrode 105b to the reference electrode 107 when the rate of decrease in the concentration of a product produced by the reduction reaction of carbon dioxide at the reduction electrode 105b exceeds a first threshold value X, and connects the reduction electrode 105b to the oxidation electrode 104 when the amount of change in the potential difference between the reduction electrode 105b and the reference electrode 107 falls below a second threshold value Y, by the control device 40 or a user.
  • the light energy and electrical energy provided during the redox reaction can be used efficiently for a long period of time in the carbon dioxide reduction reaction, without wasting it in side reactions.
  • the energy not consumed in the redox reaction during standby time can be stored or used for other purposes, making it possible to make effective use of energy.
  • artificial photosynthesis technology that utilizes solar energy can be effectively used when the reaction time and standby time cycles described in Examples 1 and 2 are shorter than the sunlight cycle of the land where the carbon dioxide gas phase reduction device 10 is used.
  • System 10 Carbon dioxide gas phase reduction device 20: Concentration measurement device 30: Electrochemical measurement device 40: Control device 101: Oxidation cell 102: Reduction cell 103: Aqueous solution 104: Oxidation electrode 105: Reduction electrode/electrolyte membrane composite 105a: Electrolyte membrane 105b: Reduction electrode 106: Switch 107: Reference electrode 108: Voltmeter 109: Light source 110: Tube 111: Gas input port 112: Gas output port 113: Power source

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Analytical Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Selon l'invention, un appareil de réduction de phase gazeuse 1 pour dioxyde de carbone réduit le dioxyde de carbone dans une phase gazeuse, et comprend : un réservoir d'oxydation 101 comprenant une électrode d'oxydation et une électrode de référence; un réservoir de réduction 102 auquel du dioxyde de carbone est fourni; un composite 105 qui est disposé entre le réservoir d'oxydation et le réservoir de réduction, et dans lequel un film d'électrolyte et une électrode de réduction sont réunis l'un à l'autre, et le film d'électrolyte est disposé sur le côté réservoir d'oxydation et l'électrode de réduction est disposée sur le côté réservoir de réduction; et un commutateur 106 qui connecte l'électrode de réduction à l'électrode d'oxydation ou à l'électrode de référence. Sous la commande d'un dispositif de commande ou d'un utilisateur, le commutateur connecte l'électrode de réduction à l'électrode d'oxydation, connecte l'électrode de réduction à l'électrode de référence si le taux de diminution de la concentration d'un produit généré par une réaction de réduction du dioxyde de carbone à l'électrode de réduction devient supérieur à un premier seuil, et connecte l'électrode de réduction à l'électrode d'oxydation si le niveau de changement de la différence de potentiel électrique entre l'électrode de réduction et l'électrode de référence devient inférieur à un second seuil.
PCT/JP2022/043751 2022-11-28 2022-11-28 Appareil de réduction de phase gazeuse pour dioxyde de carbone WO2024116235A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/043751 WO2024116235A1 (fr) 2022-11-28 2022-11-28 Appareil de réduction de phase gazeuse pour dioxyde de carbone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/043751 WO2024116235A1 (fr) 2022-11-28 2022-11-28 Appareil de réduction de phase gazeuse pour dioxyde de carbone

Publications (1)

Publication Number Publication Date
WO2024116235A1 true WO2024116235A1 (fr) 2024-06-06

Family

ID=91323264

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/043751 WO2024116235A1 (fr) 2022-11-28 2022-11-28 Appareil de réduction de phase gazeuse pour dioxyde de carbone

Country Status (1)

Country Link
WO (1) WO2024116235A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154900A (ja) * 2017-03-21 2018-10-04 株式会社東芝 電気化学反応装置と電気化学反応方法
JP2019167557A (ja) * 2018-03-22 2019-10-03 株式会社東芝 二酸化炭素電解装置および二酸化炭素電解方法
JP2020045527A (ja) * 2018-09-19 2020-03-26 株式会社東芝 電気化学反応装置
JP2021521328A (ja) * 2018-04-17 2021-08-26 レプソル，エス．エー． 光起電力−電気化学（ｐｖ−ｅｃ）システム
JP2022513860A (ja) * 2018-12-18 2022-02-09 オプス－１２ インコーポレイテッド 電解槽及び使用方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154900A (ja) * 2017-03-21 2018-10-04 株式会社東芝 電気化学反応装置と電気化学反応方法
JP2019167557A (ja) * 2018-03-22 2019-10-03 株式会社東芝 二酸化炭素電解装置および二酸化炭素電解方法
JP2021521328A (ja) * 2018-04-17 2021-08-26 レプソル，エス．エー． 光起電力−電気化学（ｐｖ−ｅｃ）システム
JP2020045527A (ja) * 2018-09-19 2020-03-26 株式会社東芝 電気化学反応装置
JP2022513860A (ja) * 2018-12-18 2022-02-09 オプス－１２ インコーポレイテッド 電解槽及び使用方法

Similar Documents

Publication Publication Date Title
WO2020121556A1 (fr) Dispositif de réduction de dioxyde de carbone en phase gazeuse et procédé de réduction de dioxyde de carbone en phase gazeuse
JP7204620B2 (ja) 電気化学反応装置
EP3626858B1 (fr) Dispositif d'électrolyse au dioxyde de carbone et procédé d'électrolyse de dioxyde de carbone
JP6951310B2 (ja) 電気化学反応装置
CN104064792B (zh) 一种高温电解水蒸汽同步氧化甲烷制备燃料的方法
JP6997376B2 (ja) 二酸化炭素還元装置
JP6221067B2 (ja) ギ酸生成装置および方法
WO2024116235A1 (fr) Appareil de réduction de phase gazeuse pour dioxyde de carbone
JP7273346B2 (ja) 二酸化炭素の気相還元方法
US20230119993A1 (en) Carbon dioxide treatment device, carbon dioxide treatment method, and method for producing carbon compound
WO2022249276A1 (fr) Dispositif de réduction de phase gazeuse pour dioxyde de carbone et procédé de réduction de phase gazeuse pour dioxyde de carbone
WO2022113277A1 (fr) Dispositif de réduction en phase gazeuse pour le dioxyde de carbone et procédé de production d'une membrane électrolytique supportée par une électrode de réduction poreuse
JP2016024924A (ja) 燃料電池システムの起動方法
WO2022244234A1 (fr) Membrane électrolytique de support d'électrode poreuse et procédé de production de membrane électrolytique de support d'électrode poreuse
WO2023084683A1 (fr) Membrane électrolytique
WO2023095203A1 (fr) Procédé de production d'une membrane électrolytique supportant une électrode poreuse
WO2023095193A1 (fr) Membrane électrolytique de support d'électrode poreuse et procédé de production d'une membrane électrolytique de support d'électrode poreuse
JP7356067B2 (ja) 二酸化炭素の気相還元装置、および、二酸化炭素の気相還元方法
WO2021234908A1 (fr) Dispositif de réduction en phase vapeur pour dioxyde de carbone et méthode de production d'une membrane électrolytique supportée par une électrode poreuse
EP1736436A1 (fr) Système d"approvisionnement d"hydrogène
JP7504849B2 (ja) 二酸化炭素電解装置、二酸化炭素電解方法、及び有価物製造システム
WO2022118364A1 (fr) Procédé de fabrication d'électrode de réduction portée sur film d'électrolyte
WO2023095201A1 (fr) Membrane électrolytique de support d'électrode poreuse et procédé de production de membrane électrolytique de support d'électrode poreuse
WO2022249314A1 (fr) Dispositif de réduction de dioxyde de carbone
WO2024116355A1 (fr) Appareil de réduction de dioxyde de carbone

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22967072

Country of ref document: EP

Kind code of ref document: A1