Carbon dioxide electrocatalytic reduction reaction device and method

Abstract

The invention provides a tandem type carbon dioxide electrocatalytic reduction reaction device which adopts a three-liquid-phase flow channel design, a CO2 saturated electrolyte flow channel, an alkaline electrolyte flow channel and an anolyte flow channel are arranged in the same reactor, and a CO selective catalyst, an alcohol selective catalyst and an anode catalyst are selected and used in a targeted manner, so that the carbon dioxide electrocatalytic reduction reaction device is obtained. According to the device, CO generation and alcohol conversion can be integrated and coordinated in the same reactor, two-step efficient conversion of CO2 to alcohol is promoted, and the device is simple and flexible in structure and wide in applicability.

Description

Technical Field

[0001] The present disclosure relates to the technical field of carbon capture and utilization, and particularly, to an apparatus and method for electrocatalytic reduction of carbon dioxide. Background Art

[0002] With the rapid development of industrial modernization, fuel shortage and environmental protection have become important issues. As the main representative component of greenhouse gases, capturing and utilizing CO2 to convert it into hydrocarbon fuels is of great significance. The basic concept of carbon capture, utilization, and storage (CCUS) technology is to capture carbon dioxide and directly utilize or store the captured carbon dioxide.

[0003] In existing CCU technologies, CO2 electrocatalytic reduction technology uses excess renewable electricity as energy to achieve chemical energy storage. The reaction is carried out at normal temperature and pressure, and can achieve an artificial closed carbon cycle, having broad industrial application prospects. Among various CO2 electrocatalytic reduction products, alcohol products such as methanol and ethanol are considered ideal energy storage forms due to their low toxicity, easy storage, wide adaptability, and high energy density. However, current CO2 electrocatalytic reduction technology for producing alcohols generally has problems such as low conversion rate, poor selectivity, low current density, and serious carbonate formation / CO2 crossover, which limit the popularization and application of related technologies. To effectively avoid the above problems, technicians have proposed a two-step route for electrochemically reducing CO2 to alcohols. CO2 is first reduced to CO in a non-alkaline electrolyte, and then the generated CO is converted into alcohol products in an alkaline electrolyte. This method can significantly and effectively improve the selectivity and conversion rate of alcohol products, and there is no problem of carbonate formation / CO2 crossover. Current related research mainly focuses on the design and optimization of electrode catalyst materials themselves. However, a complete CO2 electrocatalytic reduction technology process consists of multiple parts. Besides the catalyst material itself, the type of electrolyte, the selection of ion exchange membrane, the design of electrolytic cell structure, etc. may all have a direct impact on the overall performance of the technology process. Currently, the two-step electrochemically reducing CO2 to alcohols is mainly carried out in two different reaction systems respectively, having the problem of complex reaction systems.

[0004] Therefore, there is an urgent need to provide an apparatus and method applicable to the two-step process, which can realize the coordinated generation of CO and the conversion of alcohols in the same reactor, so as to promote the efficient two-step conversion of CO2 to alcohols. Summary of the Invention

[0005] The purpose of the present disclosure is to provide an apparatus and method applicable to the two-step process, which can realize the coordinated generation of CO and the conversion of alcohols in the same reactor, so as to promote the efficient two-step conversion of CO2 to alcohols.

[0006] To achieve the above object, the present disclosure provides a device for electrocatalytic reduction of carbon dioxide, and the device includes a reactor; Inside the reactor, a CO2 saturated electrolyte flow channel (2), a first gas diffusion layer (3), an alkaline electrolyte flow channel (5), a second gas diffusion layer (6), an anion exchange membrane (8), a third gas diffusion layer (10), and an anolyte flow channel (11) are sequentially arranged from top to bottom in the vertical direction; On one side of the first gas diffusion layer (3) facing the alkaline electrolyte flow channel (5), a CO selective catalyst (4) is coated; On one side of the second gas diffusion layer (6) facing the anion exchange membrane (8), an alcohol selective catalyst (7) is coated; On one side of the third gas diffusion layer (10) facing the anion exchange membrane (8), an anode electrocatalyst (9) is coated.

[0007] Optionally, the reactor further includes a reduction side outer wall (1), a reduction side inner wall (15), and an oxidation side outer wall (12); Inside the reactor, a reduction side outer wall (1), a CO2 saturated electrolyte flow channel (2), a first gas diffusion layer (3), an alkaline electrolyte flow channel (5), a reduction side inner wall (15), a second gas diffusion layer (6), an anion exchange membrane (8), a third gas diffusion layer (10), an anolyte flow channel (11), and an oxidation side outer wall (12) are sequentially arranged from top to bottom in the vertical direction; A CO2 saturated electrolyte inlet (16) and a CO2 saturated electrolyte outlet (19) are provided on the reduction side outer wall (1); An alkaline electrolyte inlet (17) and an alkaline electrolyte outlet (20) are provided on the reduction side inner wall (15); An anolyte inlet (18) and an anolyte outlet (21) are provided on the oxidation side outer wall (12); Wherein, the alkaline electrolyte flow channel at the reduction side inner wall (15) is a through-flow channel.

[0008] Optionally, the CO selective catalyst (4) is any one or several selected from Ag nanoparticles, Au nanoparticles, and Pd nanoparticles; The alcohol selective catalyst (7) is any one or several selected from Rh1Cu4 alloy, B-CoPc / NC, and Cu / ZnS; The anode electrocatalyst (9) is any one or several selected from IrOx, V2O5, and Pt.

[0009] Optionally, the CO selective catalyst (4) is selected from Ag nanoparticles; the alcohol selective catalyst (7) is selected from Rh1Cu4 alloy; the anode electrocatalyst (9) is selected from IrOx.

[0010] The CO2 saturated electrolyte in the CO2 saturated electrolyte flow channel (2) is a CO2 saturated KHCO3 solution; the alkaline electrolyte in the alkaline electrolyte flow channel (5) is a KOH solution; the anode electrolyte in the anode electrolyte flow channel (11) is a KOH solution.

[0011] A reduction side current collector plate (13) and an oxidation side current collector plate (14) are respectively arranged on the upper parts of the reduction side outer wall (1) and the oxidation side outer wall (12) for wire connection to apply an electric field.

[0012] Optionally, the reduction side outer wall (1), the reduction side inner wall (15), and the oxidation side outer wall (12) are made of conductive metal, preferably titanium plates; The reduction side current collector plate (13) and the oxidation side current collector plate (14) are made of conductive metal, preferably Cu.

[0013] On the other hand, the present disclosure provides a method for electrocatalytic reduction of carbon dioxide, using the device described in the first aspect of the present disclosure, including the following steps: Let the CO2 saturated electrolyte enter the CO2 saturated electrolyte flow channel (2) from the CO2 saturated electrolyte inlet (16), apply an electric field through the reduction side current collector plate (13) and the oxidation side current collector plate (14), and allow CO2 to diffuse to the first gas diffusion layer (3) to contact the CO selective catalyst (4) for an electrocatalytic reduction reaction to generate CO gas; Let the CO gas diffuse to the second gas diffusion layer (6), contact the alcohol catalyst (7) for an electrocatalytic reduction reaction to generate methanol and OH - ; the methanol is discharged from the reactor through the alkaline electrolyte outlet (17); Let the OH - Diffuse through the anion exchange membrane (8) to the third gas diffusion layer (10), contact the anode electrocatalyst (9) for an oxygen evolution reaction to generate O2 gas; Let the O2 gas enter the anode electrolyte flow channel (11) through the third gas diffusion layer (10) and be discharged from the reactor along with the anode electrolyte.

[0014] Through the above technical solutions, the present disclosure provides a tandem-type carbon dioxide electrocatalytic reduction reaction device and method. In this device, the CO2-saturated electrolyte flow channel, the alkaline electrolyte flow channel, and the anode electrolyte flow channel are arranged in the same reactor, enabling the generation of CO and the conversion of alcohols to be coordinated in the same reactor, thereby promoting the two-step efficient conversion of CO2 to alcohols. Moreover, the device has a simple structure, can be flexibly adjusted, and has a wide applicability.

[0015] Other features and advantages of the present disclosure will be described in detail in the following specific implementation section. Brief Description of the Drawings

[0016] The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific implementation, they are used to explain the present invention, but do not constitute a limitation to the present invention. In the drawings: Figure 1 It is a schematic structural composition diagram of the reactor in the electrocatalytic reduction device of Example 1; Figure 2 It is a schematic overall appearance diagram of the reactor in the electrocatalytic reduction device of Example 1; Figure 3 It is a schematic internal cross-section and mass transfer diagram of the reactor in the electrocatalytic reduction device of Example 1.

[0017] Reference Signs 1 - Outer wall of the reduction side; 2 - CO2-saturated electrolyte flow channel; 3 - First gas diffusion layer; 4 - CO-selective electrocatalyst; 5 - Alkaline electrolyte flow channel; 6 - Second gas diffusion layer; 7 - Alcohol-selective electrocatalyst; 8 - Anion exchange membrane; 9 - Anode electrocatalyst; 10 - Third gas diffusion layer; 11 - Anode electrolyte flow channel; 12 - Outer wall of the oxidation side; 13 - Reduction-side current collector plate; 14 - Oxidation-side current collector plate; 15 - Inner wall of the reduction side; 16 - CO2-saturated electrolyte inlet; 17 - Alkaline electrolyte flow channel inlet; 18 - Anode electrolyte inlet; 19 - CO2-saturated electrolyte outlet; 20 - Alkaline electrolyte flow channel outlet; 21 - Anode electrolyte outlet; 22 - Fixed bolt (hole). Specific Embodiments

[0018] The following provides a detailed description of the specific embodiments of the present disclosure. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure and do not limit the present disclosure.

[0019] The present disclosure provides a device for electrocatalytic reduction of carbon dioxide. The device includes a reactor. Inside the reactor, a CO2-saturated electrolyte flow channel 2, a first gas diffusion layer 3, an alkaline electrolyte flow channel 5, a second gas diffusion layer 6, an anion exchange membrane 8, a third gas diffusion layer 10, and an anolyte flow channel 11 are sequentially arranged from top to bottom in the vertical direction. On one side of the first gas diffusion layer 3 facing the alkaline electrolyte flow channel 5, a CO-selective catalyst 4 is coated. On one side of the second gas diffusion layer 6 facing the anion exchange membrane 8, an alcohol-selective electrocatalyst 7 is coated. On one side of the third gas diffusion layer 10 facing the anion exchange membrane 8, an anode electrocatalyst 9 is coated.

[0020] By arranging the CO2-saturated electrolyte flow channel, the alkaline electrolyte flow channel, and the anolyte flow channel in the same reactor, the present disclosure can realize the coordinated progress of CO2 generation of CO and CO generation of alcohols in the same reactor, promote the two-step efficient conversion of CO2 to alcohols; the device has a simple structure, and the composition of the electrolyte in the relevant flow channels and the selection of catalysts can be flexibly adjusted according to actual needs, so that the most sufficient electrocatalytic reduction reaction can be realized in different practical processes, improving the universality of the device.

[0021] The first gas diffusion layer, the second gas diffusion layer, and the third gas diffusion layer of the present disclosure are prepared by selecting materials such as carbon fiber paper, carbon fiber woven cloth, and carbon black paper, and are sprayed with polytetrafluoroethylene on the surface, having hydrophobic properties, thereby avoiding the intrusion of liquid electrolyte.

[0022] Optionally, the reactor further includes a reduction-side outer wall 1, a reduction-side inner wall 15, and an oxidation-side outer wall 12. Inside the reactor, a reduction-side outer wall 1, a CO2-saturated electrolyte flow channel 2, a first gas diffusion layer 3, an alkaline electrolyte flow channel 5, a reduction-side inner wall 15, a second gas diffusion layer 6, an anion exchange membrane 8, a third gas diffusion layer 10, an anolyte flow channel 11, and an oxidation-side outer wall 12 are sequentially arranged from top to bottom in the vertical direction. A CO2-saturated electrolyte inlet 16 and a CO2-saturated electrolyte outlet 19 are provided on the reduction-side outer wall 1. An alkaline electrolyte inlet 17 and an alkaline electrolyte outlet 20 are provided on the reduction-side inner wall 15. An anolyte inlet 18 and an anolyte outlet 21 are provided on the oxidation-side outer wall 12. Among them, the alkaline electrolyte flow channel at the reduction-side inner wall 15 is a through-flow channel.

[0023] The device described in the present disclosure further includes common combined components in an electrocatalytic reduction reaction device such as electrodes and electrolytes. Meanwhile, the electrocatalytic reduction reaction conditions all belong to the scope of conventional operations in the art and can be adjusted according to actual needs.

[0024] In the present disclosure, the shapes of the respective flow channels can be selected according to specific requirements, and preferably a serpentine flow channel is used to increase the contact area between the catalyst and the reactant, enabling the two to come into full contact.

[0025] The through-flow channel described in the present disclosure, that is, the alkaline electrolyte flow channel at the inner wall 15 of the reduction side, is a continuous and unobstructed flow channel, enabling the alkaline electrolyte to flow smoothly in this area, uniformly distributed around the inner wall of the reduction side, and increasing the reaction contact area and contact time.

[0026] In one embodiment, the CO2-saturated electrolyte enters the CO2-saturated electrolyte flow channel 2 from the CO2-saturated electrolyte inlet 16, where CO2 diffuses to the gas diffusion layer 3 and contacts the CO selective catalyst 4 to undergo an electrocatalytic reduction reaction to generate CO gas; The CO gas diffuses to the gas diffusion layer 6 coated with the alcohol catalyst 7 and contacts the alcohol catalyst 7 to undergo an electrocatalytic reduction reaction to generate methanol and OH - ; the methanol is discharged from the reactor through the alkaline electrolyte outlet 17; The OH - diffuses through the anion exchange membrane 8 to the gas diffusion layer 10 coated with the anode electrocatalyst 9 and contacts the anode electrocatalyst 9 to undergo an oxygen evolution reaction to generate O2 gas; The O2 gas enters the anode electrolyte flow channel 11 through the gas diffusion layer 10 and is discharged from the reactor along with the anode electrolyte.

[0027] In one embodiment, the CO selective catalyst 4 is any one or several selected from Ag nanoparticles, Au nanoparticles, and Pd nanoparticles; the alcohol selective catalyst 7 is any one or several selected from Rh1Cu4 alloy, B-CoPc / NC, and Cu / ZnS; the anode electrocatalyst 9 is any one or several selected from IrOx, V2O5, and Pt.

[0028] In a preferred embodiment, the CO selective catalyst 4 is Ag nanoparticles; the alcohol selective catalyst 7 is Rh1Cu4 alloy; the anode electrocatalyst 9 is IrOx.

[0029] In one embodiment, the CO2-saturated electrolyte is any electrolyte that can support the conversion of CO2 to CO under the action of a catalyst, and preferably a CO2-saturated KHCO3 solution; The alkaline electrolyte can be any electrolyte that supports the conversion of CO to alcohols under the action of a catalyst, preferably a KOH solution; The anolyte is any electrolyte that supports the oxygen evolution reaction under the action of a catalyst, preferably a KOH solution.

[0030] In one embodiment, a reduction-side current collector plate 13 and an oxidation-side current collector plate 14 are respectively provided on the upper parts of the reduction-side outer wall 1 and the oxidation-side outer wall 12 for connecting wires to apply an electric field; In one embodiment, the reduction-side outer wall 1, the reduction-side outer wall 15, and the oxidation-side outer wall 12 are made of a conductive metal, preferably a titanium plate; the reduction-side current collector plate 13 and the oxidation-side current collector plate 14 are made of a conductive metal, preferably Cu.

[0031] In one embodiment, a plurality of fixing bolts (holes) 22 are further provided on the reduction-side outer wall 1, the reduction-side inner wall 15, and the oxidation-side outer wall 12 for assembling and fixing each component of the reactor, maintaining the stable structure of the reactor and the shapes of each flow channel, ensuring the integrity and tightness of the flow channel, preventing electrolyte leakage, and ensuring that the reaction proceeds orderly within the specified flow channel.

[0032] On the other hand, the present disclosure provides a method for electrocatalytic reduction of carbon dioxide, which uses the device described in the first aspect of the present disclosure and includes the following steps: Let the CO2-saturated electrolyte enter the CO2-saturated electrolyte flow channel 2 from the CO2-saturated electrolyte inlet 16, apply an electric field through the reduction-side current collector plate 13 and the oxidation-side current collector plate 14, and allow CO2 to diffuse to the first gas diffusion layer 3 to contact the CO selective catalyst 4 for an electrocatalytic reduction reaction to generate CO gas; Let the CO gas diffuse to the second gas diffusion layer 6 and contact the alcohol catalyst for an electrocatalytic reduction reaction to generate methanol and OH - ; the methanol is discharged from the reactor through the alkaline electrolyte outlet 17; Let the OH - diffuse through the anion exchange membrane 8 to the third gas diffusion layer 10 and contact the anode electrocatalyst 9 for an oxygen evolution reaction to generate O2 gas; Let the O2 gas enter the anolyte flow channel 11 through the third gas diffusion layer 10 and be discharged from the reactor with the anolyte.

[0033] The present invention is further described in detail below through examples.

[0034] Example 1 This example provides a tandem electrocatalytic reduction reaction device for carbon dioxide, which includes a reactor, and the structural composition of the reactor is asFigure 1 As shown, the overall appearance is as Figure 2 shown, and the internal cross-section and mass transfer schematic diagram are as Figure 3 shown.

[0035] Inside the reactor, a reduction-side outer wall 1, a CO2-saturated electrolyte flow channel 2, an alkaline electrolyte flow channel 5, a reduction-side inner wall 15, an anolyte flow channel 11, and an oxidation-side outer wall 12 are successively arranged from top to bottom; the CO2-saturated electrolyte flow channel 2 and the alkaline electrolyte flow channel 5 are separated by a first gas diffusion layer 3 coated with a CO selective catalyst 4; between the alkaline electrolyte flow channel 5 and the anolyte flow channel 11, there are separated by a second gas diffusion layer 6 coated with an alcohol selective catalyst 7, an anion exchange membrane 8, and a third gas diffusion layer 10 coated with an anode electrocatalyst 9, which are arranged in sequence from top to bottom; On the reduction-side outer wall 1, a CO2-saturated electrolyte inlet 16 and a CO2-saturated electrolyte outlet 19 are provided; on the reduction-side inner wall 15, an alkaline electrolyte inlet 17 and an alkaline electrolyte outlet 20 are provided; on the oxidation-side outer wall 12, an anolyte inlet 18 and an anolyte outlet 21 are provided; the alkaline electrolyte flow channel at the reduction-side inner wall 15 is a through type; on the upper parts of the reduction-side outer wall 1 and the oxidation-side outer wall 12, a current collector plate 13 (Cu) and a current collector plate 14 (Cu) are respectively provided. The cathode (the gas diffusion layer 3 coated with a CO selective catalyst 4) is connected to the reduction-side current collector plate 13 on the reduction-side outer wall 1, and the anode (the gas diffusion layer 10 coated with an anode electrocatalyst 9) is connected to the oxidation-side current collector plate 14 on the oxidation-side outer wall 12 and is connected to an external electric field through a wire; on the reduction-side outer wall 1 (titanium plate), the reduction-side inner wall 15 (titanium plate), and the oxidation-side outer wall 12 (titanium plate), there are also provided a plurality of fixing bolts (holes) 22 for assembling and fixing each component of the reactor, maintaining the stable structure of the reactor and the shape of each flow channel, ensuring the integrity and tightness of the flow channel, preventing electrolyte leakage, and ensuring that the reaction proceeds orderly within the specified flow channel.

[0036] The CO2-saturated electrolyte enters the CO2-saturated electrolyte flow channel 2 from the CO2-saturated electrolyte inlet (1M CO2-saturated KHCO3 solution) 16. Among them, CO2 diffuses to the gas diffusion layer 3 and contacts the CO selective catalyst 4 (nano-Ag particles) to undergo an electrocatalytic reduction reaction to generate CO gas; the CO gas diffuses to the gas diffusion layer 6 coated with an alcohol catalyst 7 and contacts the alcohol catalyst 7 (Rh1Cu4 alloy) to undergo an electrocatalytic reduction reaction to generate methanol and OH - ; the methanol is discharged from the reactor through the alkaline electrolyte (1M KOH solution) outlet 17; OH -It diffuses through the anion exchange membrane 8 to the gas diffusion layer 10 coated with the anode electrocatalyst 9 (IrOx), and the oxygen evolution reaction occurs upon contact with the anode electrocatalyst 9 (IrOx) to generate O2 gas; the O2 gas enters the anode electrolyte (1M KOH solution) flow channel 11 through the gas diffusion layer 10 and is discharged from the reactor along with the anode electrolyte.

[0037] The CO2 electrocatalytic reduction reaction device further includes a product storage tank, which is connected to the alkaline electrolyte outlet 17 and is used to collect methanol.

[0038] The preferred embodiments of the present disclosure have been described in detail above. However, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept scope of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure. In addition, it should be noted that, among the various specific technical features described in the above specific embodiments, they can be combined in any appropriate manner without conflict. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination methods.

[0039] Furthermore, any combination can be made among various different embodiments of the present disclosure as long as it does not violate the idea of the present disclosure, and it should also be regarded as the content disclosed by the present disclosure.

Claims

1. An electrocatalytic reduction reaction device for carbon dioxide, characterized in that, The device includes a reactor; Inside the reactor, a CO2-saturated electrolyte flow channel (2), a first gas diffusion layer (3), an alkaline electrolyte flow channel (5), a second gas diffusion layer (6), an anion exchange membrane (8), a third gas diffusion layer (10), and an anolyte flow channel (11) are sequentially arranged from top to bottom in the vertical direction; On one side of the first gas diffusion layer (3) facing the alkaline electrolyte flow channel (5), a CO selective catalyst (4) is coated; On one side of the second gas diffusion layer (6) facing the anion exchange membrane (8), an alcohol selective electrocatalyst (7) is coated; On one side of the third gas diffusion layer (10) facing the anion exchange membrane (8), an anode electrocatalyst (9) is coated.

2. The device according to claim 1, wherein The reactor also includes a reduction-side outer wall (1), a reduction-side inner wall (15), and an oxidation-side outer wall (12); Inside the reactor, a reduction-side outer wall (1), a CO2-saturated electrolyte flow channel (2), a first gas diffusion layer (3), an alkaline electrolyte flow channel (5), a reduction-side inner wall (15), a second gas diffusion layer (6), an anion exchange membrane (8), a third gas diffusion layer (10), an anolyte flow channel (11), and an oxidation-side outer wall (12) are sequentially arranged from top to bottom in the vertical direction; A CO2-saturated electrolyte inlet (16) and a CO2-saturated electrolyte outlet (19) are provided on the reduction-side outer wall (1); An alkaline electrolyte inlet (17) and an alkaline electrolyte outlet (20) are provided on the reduction-side inner wall (15); An anolyte inlet (18) and an anolyte outlet (21) are provided on the oxidation-side outer wall (12); Among them, the alkaline electrolyte flow channel at the reduction-side inner wall (15) is a through-flow channel.

3. The apparatus according to claim 1, wherein, The CO selective catalyst (4) is any one or several selected from Ag nanoparticles, Au nanoparticles, and Pd nanoparticles; The alcohol selective catalyst (7) is any one or several selected from Rh1Cu4 alloy, B-CoPc / NC, and Cu / ZnS; The anode electrocatalyst (9) is any one or several selected from IrOx, V2O5, and Pt.

4. The device according to claim 3, wherein, The CO selective catalyst (4) is Ag nanoparticles; the alcohol selective catalyst (7) is Rh1Cu4 alloy; the anode electrocatalyst (9) is IrOx.

5. The device according to claim 2, wherein The CO2-saturated electrolyte in the CO2-saturated electrolyte flow channel (2) is a CO2-saturated KHCO3 solution; the alkaline electrolyte in the alkaline electrolyte flow channel (5) is a KOH solution; the anolyte in the anolyte flow channel (11) is a KOH solution.

6. The device according to claim 2, wherein, A reduction-side current collector plate (13) and an oxidation-side current collector plate (14) are respectively provided on the upper parts of the reduction-side outer wall (1) and the oxidation-side outer wall (12) for wire connection to apply an electric field.

7. The apparatus according to claim 6, wherein, The reduction-side outer wall (1), the reduction-side inner wall (15), and the oxidation-side outer wall (12) are made of conductive metal, preferably titanium plates.

8. The apparatus according to claim 6, wherein, The reduction-side current collector plate (13) and the oxidation-side current collector plate (14) are made of conductive metal, preferably Cu.

9. A method for electrocatalytic reduction reaction of carbon dioxide, characterized in that, Using the device according to any one of claims 1-8, comprising the following steps: Let the CO2-saturated electrolyte enter the CO2-saturated electrolyte flow channel (2) from the CO2-saturated electrolyte inlet (16), apply an electric field through the reduction-side current collector plate (13) and the oxidation-side current collector plate (14), and allow the CO2 to diffuse to the first gas diffusion layer (3) to contact the CO selective catalyst (4) to undergo an electrocatalytic reduction reaction to generate CO gas; Diffuse the CO gas to the second gas diffusion layer (6), and contact with the alcohol catalyst (7) to carry out an electrocatalytic reduction reaction to generate methanol and OH - ; The methanol is discharged from the reactor through the alkaline electrolyte outlet (17); Cause the OH - diffuse through the anion exchange membrane (8) to the third gas diffusion layer (10), contact with the anode electrocatalyst (9) to undergo an oxygen evolution reaction, and generate O2 gas; Let the O2 gas enter the anode electrolyte flow channel (11) through the third gas diffusion layer (10) and be discharged from the reactor along with the anode electrolyte.

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