A trinuclear copper cluster atomic level catalyst, a preparation method and application thereof

Abstract

The present application is directed to the field of green electrocatalytic conversion, and relates to a kind of trinuclear copper cluster atomic level catalyst and its preparation method and application, specifically applied to the field of electrocatalytic carbon dioxide reduction (ECO2RR). The present application first prepares copper-based metal-organic compound precursor (Cu3-NF), selects graphene oxide (GO) as the carrier, disperses Cu3-NF and GO uniformly in an organic solvent to obtain a suspension, due to the physical / chemical adsorption between the two, and obtains Cu3-NF- GO composite material after drying. Finally, Cu3-NF- GO is pyrolyzed in a inert protective atmosphere at a second level to obtain a graphene-supported trinuclear copper cluster catalyst (Cu3-NG). Cu3-NG has multiple active centers including top and bridging sites, provides multiple adsorption modes for CO2 and intermediates, and can generate high-value C2 product ethanol with high selectivity. The preparation method of the present application significantly suppresses the adverse atomic group aggregation phenomenon, improves the controllability of synthesizing a clear trinuclear structure, and is expected to promote the industrialization process of electrocatalytic carbon dioxide reduction.

Description

Technical Field

[0001] This invention targets the field of green and sustainable electrocatalytic conversion, specifically a trinuclear copper cluster atomic-level catalyst for the electrocatalytic reduction of carbon dioxide. The material synthesis method in this invention significantly reduces the generation of non-target metal nanoparticles, improving the controllability of atomic-level catalyst preparation. This trinuclear copper cluster atomic-level catalyst can achieve highly selective electrocatalytic reduction of CO2 molecules to the economically valuable C2 product ethanol, with weak hydrogen evolution side reactions and high overall CO2 conversion efficiency. Background Technology

[0002] Besides natural pathways such as carbon capture and storage through bioenergy, industrial technologies urgently need to be developed and promoted to recycle and utilize redundant carbon emissions. Furthermore, the non-renewable nature of fossil fuels is leading to the depletion of their earthly reserves, making the solution to the energy crisis an urgent matter. As an ideal solution, electrocatalytic carbon dioxide reduction can not only close the artificial carbon cycle but also convert renewable energy sources such as solar and wind energy into chemical energy stored in high-value-added products, including clean fuels and industrial raw materials, thus achieving a virtuous cycle of turning waste into treasure. In addition, electrocatalytic carbon dioxide reduction also boasts numerous technological advantages, including mild reaction conditions (it can be carried out under normal temperature and pressure), high controllability (the type, selectivity, and conversion rate of products can be adjusted by changing the applied potential and electrolyte alkalinity), and highly modular reaction equipment suitable for large-scale industrial applications.

[0003] However, the high C=O bond energy barrier and thermodynamic stability of the CO2 molecule make it difficult to activate. Furthermore, the complexity of the electrocatalytic carbon dioxide reduction reaction mechanism is considerable, involving multiple proton-coupled electron transfer processes. To date, research in the field of electrocatalytic carbon dioxide reduction is still in its nascent stage and far less mature than other electrochemical technologies such as water electrolysis for hydrogen production and fuel cells. Currently reported conversion products are mostly limited to C1 products such as CO, CH4, and HCOOH. Besides the hydrogen evolution reaction being the main competing reaction, there is also significant competition among different reduction products due to their similar equilibrium potentials. Therefore, developing stable catalysts with both high electrochemical activity and high selectivity for target products is a prerequisite for the practical application of electrocatalytic carbon dioxide reduction. It is worth noting that multi-carbon products with higher economic value generally only form on the surface of copper-based catalysts, making them the optimal choice for electrocatalytic carbon dioxide reduction catalysts. For example, patent application CN118272859A discloses a catalyst for the electrocatalytic reduction of carbon dioxide to ethylene and its preparation method, which uses copper oxide nanoparticles as a substrate doped with trace amounts of lanthanum to electrocatalytically reduce CO2 to C2 ethylene. However, liquid C2 products such as ethanol are more economically valuable and are more ideal reduction products. Triatomic catalysts, while retaining the advantages of easily adjustable coordination structures and 100% atomic utilization of single-atom catalysts, offer greater flexibility in controlling the geometry and electronic structure of their metal active centers. Furthermore, the unique synergistic effect between multiple metal atoms allows them to break through the theoretical limits of catalytic performance of single-atom materials. However, the synthesis of multi-atom catalysts is less controllable, and they are prone to aggregation during preparation, resulting in the formation of undesirable nanoparticles. Patent application CN111659423B, entitled "A Preparation Method and Application Method of a Cobalt-Tellulose Diatomic Site Catalyst," primarily utilizes the confinement effect of ZIF-8 to encapsulate metal precursors as a "cage," preventing the migration and aggregation of metal atoms during subsequent pyrolysis to remove ligands. However, the preparation process of ZIF materials is cumbersome, and its encapsulation size is not perfectly adapted to any metal precursor. This indicates that the size of the "cage" and the precursor needs to be highly compatible, resulting in significant limitations in the application of this process and hindering large-scale industrial production. Therefore, the application of multiatomic catalysts in the field of electrocatalysis is still in its infancy, and its application in electrocatalytic carbon dioxide reduction is even rarer. Summary of the Invention

[0004] Based on the current technical challenges and application limitations of multi-atom material synthesis, we designed a second-level pyrolysis imprinting technique to synthesize trinuclear copper cluster atomic-level catalysts. This technique not only has a simple preparation process but also effectively avoids unfavorable atomic aggregation. It also largely preserves the coordination structure of the trinuclear copper atoms in the metal-organic precursor, resulting in a high proportion of target triatomic groups in the synthesized trinuclear copper cluster catalyst. Furthermore, it exhibits excellent electrocatalytic reduction of carbon dioxide, with weak hydrogen evolution side reactions and high Faradaic efficiency in generating the economically valuable C2 product ethanol, demonstrating significant potential for large-scale industrial applications. The specific technical solution of this invention is as follows:

[0005] A trinuclear copper cluster atomic-level carbon dioxide reduction electrocatalyst: atomic-level copper ions and non-metallic nitrogen atoms are dispersed on a graphene-based support, and the copper ions are coordinated with carbon and nitrogen atoms through stable valence bonds to form a special trinuclear copper cluster structure.

[0006] The catalyst contains 0.1–10.0 wt.% copper and 0.1–20.0 wt.% nitrogen.

[0007] Synthetic route of the above catalyst:

[0008] 1) Preparation of Cu3-NF precursor: Add 0.35g CuCl2·2H2O to 50mL of deionized water and stir well to prepare solution A. Add 0.15g 1,2,4-triazole to 10mL of deionized water and stir well to prepare solution B. Mix solution A and solution B to precipitate powdery crystals (Cu3-NF).

[0009] 2) Weigh a certain amount of Cu3-NF precursor and 100mg of graphene oxide and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0010] 3) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75℃ to remove the water solvent.

[0011] 4) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0012] 5) Cu3-NF-GO material was placed in a fast-moving boat and calcined in seconds at an ultra-fast temperature of 700-200℃ under inert nitrogen protection. Cu3-NG was obtained after pyrolysis for 5 seconds.

[0013] In step 1), ensure the correct synthesis of the metal-organic complex Cu3-NF precursor.

[0014] In step 2), ensure that the Cu3-NF precursor and graphene oxide are highly uniformly dispersed in 80 mL of distilled water.

[0015] In step 2), a certain amount of Cu3-NF precursor and 100 mg of graphene oxide are weighed out. In parallel experiments, 2 mg, 6 mg, 12 mg, 18 mg or 25 mg of Cu3-NF precursor are weighed out respectively to control the copper atom loading of Cu3-NF-GO.

[0016] In step 3), ensure that the water in the suspension obtained in step 2) is completely removed after rotary evaporation.

[0017] In step 4), the black solid residue scraped from the rotary evaporation flask is ground thoroughly in an agate mortar until it becomes a black powder material (Cu3-NF-GO).

[0018] In step 5), the entire calcination process of the black Cu3-NF-GO powder must be carried out under the protection of inert nitrogen gas to avoid the formation of unfavorable oxides.

[0019] In step 5), the black Cu3-NF-GO powder needs to be heated to 1800℃ very quickly with the assistance of a fast-moving boat, and after pyrolysis is completed in 5 seconds, it is then rapidly cooled to room temperature in an inert atmosphere.

[0020] The present invention also provides the application of the above-mentioned catalyst in electrocatalytic carbon dioxide reduction.

[0021] The beneficial effects of this invention are as follows:

[0022] The trinuclear copper cluster atomic-level catalyst synthesized by this method has a high proportion of triatomic groups that retain the metal coordination structure of the precursor (Cu3-NF), and the ultrafast pyrolysis imprinting technology suppresses the generation of nanoparticles.

[0023] The heterogeneity and coordination effect between the triatomic copper and the carbon-nitrogen support in the catalyst synthesized by this method can optimize the electronic state density between active copper sites, making them charge-rich centers capable of adsorbing and activating CO2 molecules.

[0024] The trinuclear copper cluster atom catalyst synthesized by this method can achieve highly selective conversion of CO2 molecules into high-value-added C2 product ethanol, with weak hydrogen evolution reaction and extremely low generation of by-product hydrogen gas, achieving highly efficient electrocatalytic reduction of CO2 with a Faraday efficiency of nearly 90%. Attached Figure Description

[0025] To further clarify the application and performance of the technical solutions or embodiments in the preparation method of the present invention, the following drawings will be provided for further explanation;

[0026] Figure 1 This is the initial theoretical model of the catalyst in Example 1;

[0027] Figure 2 This is a theoretical model for the adsorption of electrocatalytic carbon dioxide reduction intermediates at active copper sites in the catalyst of Example 1;

[0028] Figure 3 These are the X-ray diffraction patterns of Example 1 and Comparative Examples 1 and 2;

[0029] Figure 4 These are the K-edge X-ray absorption near-edge structure spectra of Example 1 and Cu2O, CuPc and Cu foil;

[0030] Figure 5 These are transmission electron microscope images of Example 1;

[0031] Figure 6 These are aberration-corrected transmission electron microscope images from Example 1;

[0032] Figure 7 These are the linear voltammetric curves of electrocatalytic carbon dioxide reduction in Example 1 and Comparative Example 1;

[0033] Figure 8 This is a comparison of the product formation and corresponding Faraday efficiency of Example 1, Comparative Examples 1 and 2, and the leading copper-based carbon dioxide reduction electrocatalyst. Detailed Implementation

[0034] The following examples will further clarify the synthesis technique and application purpose of the present invention. It is emphasized that the examples described herein are merely supplementary explanations to provide a more intuitive understanding of the invention and are not intended to limit the scope of the invention as defined by the appended claims.

[0035] Example 1

[0036] 1) Preparation of Cu3-NF precursor: Add 0.35g CuCl2·2H2O to 50mL of deionized water and stir well to prepare solution A. Add 0.15g 1,2,4-triazole to 10mL of deionized water and stir well to prepare solution B. Mix solution A and solution B to precipitate powdery crystals (Cu3-NF).

[0037] 2) Weigh 1.0 mg of Cu3-NF precursor and 100 mg of graphene oxide and add them together to a 100 mL beaker. Then add 80 mL of distilled water to the beaker, put a magnetic ball into the beaker and stir for 10 min, and sonicate for 60 min to mix them thoroughly into a uniform suspension.

[0038] 3) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75℃ to remove the water solvent.

[0039] 4) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0040] 5) Weigh 15mg of Cu3-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5s, 1.0wt% Cu3-NG (the optimal sample is briefly referred to as Co3-NG) is obtained.

[0041] Example 2

[0042] 1) Weigh 20mg of Cu3-NF precursor and 100mg of graphene oxide and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0043] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0044] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0045] 4) Weigh 15mg of Cu3-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5 seconds, 2.0wt% Cu3-NG is obtained.

[0046] Example 3

[0047] 1) Weigh 50mg of Cu3-NF precursor and 100mg of graphene oxide and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0048] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0049] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0050] 4) Weigh 15mg of Cu3-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5s, 5.0wt% Cu3-NG is obtained.

[0051] Example 4

[0052] 1) Weigh 70mg of Cu3-NF precursor and 100mg of graphene oxide and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0053] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0054] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0055] 4) Weigh 15mg of Cu3-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5 seconds, 7.0wt% Cu3-NG is obtained.

[0056] Example 5

[0057] 1) Weigh 100mg of Cu3-NF precursor and 100mg of graphene oxide and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0058] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0059] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0060] 4) Weigh 15mg of Cu3-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5s, 10.0wt% Cu3-NG is obtained.

[0061] Comparative Example 1

[0062] 1) Weigh 12mg Cu3-NF precursor and 100mg graphene oxide together and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0063] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0064] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO).

[0065] 4) Weigh 20 mg of Cu3-NF-GO material and place it in a common ceramic boat inside a tube furnace. Under inert nitrogen protection, heat the material to 750°C at a rate of 10°C per minute and maintain the temperature for 2 hours for pyrolysis. Then, allow it to cool naturally to room temperature to obtain 2.0 wt% Cu3-NG-NP material containing a large number of nanoparticles formed by unfavorable agglomeration.

[0066] Comparative Example 2

[0067] 1) Weigh 20mg CuCl2 and 100mg graphene oxide together and add them to a 100mL beaker. Then add 80mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10min and sonicate for 60min to mix them thoroughly into a uniform suspension.

[0068] 2) Transfer the suspension to a 250mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum at 75°C to remove the water solvent.

[0069] 3) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu-GO).

[0070] 4) Collect the black powder material Cu-GO from step 3) into an agate mortar, and add 3 times the volume of melamine to Cu-GO as a nitrogen source. Continue grinding until the two are mixed evenly to obtain a grayish-white powder (Cu-NF-GO).

[0071] 4) Weigh 15mg of Cu-NF-GO material and place it in a fast-moving boat. Under inert nitrogen protection, calcine it at 1800℃ in seconds. After pyrolysis for 5 seconds, 2.0wt% Cu-NG is obtained.

[0072] Structural inspection:

[0073] Figure 1 Figure 2 The initial structure of the trinuclear copper cluster atomic-level catalyst and its reaction structure applied in electrocatalytic carbon dioxide reduction are described.

[0074] Figure 3 The XRD results showed that there were obvious diffraction peaks of Cu nanoparticles in Comparative Example 1, while there were no diffraction peaks of Cu nanoparticles in Example 1 and Comparative Example 2. This indicates that the ultrafast pyrolysis imprinting technology of the above samples effectively avoided the unfavorable agglomeration during the high-temperature calcination process.

[0075] Figure 4 XANES results of the K-edge of Cu atoms showed that, by comparing with the test spectra of standard Cu2O, Cu foil and CuPC, the copper sites in Example 1 exhibited an atomically dispersed trinuclear cluster distribution structure, rather than existing in the form of nanoparticle oxides.

[0076] Figure 5 High-resolution transmission electron microscopy images show that Cu nanoparticles are not present in the sample of Example 1.

[0077] Figure 6 The aberration-corrected transmission electron microscope images show that Example 1 has multiple three-copper atom groups distributed in a triangular pattern, which are considered to be trinuclear copper atoms. This indicates that the method effectively avoids high-temperature aggregation and successfully synthesizes trinuclear copper cluster atomic-level catalysts.

[0078] Performance testing:

[0079] To evaluate the catalytic activity of Comparative Examples 1 and 2, and Examples 1, 2, 3, 4, and 5 on ECO2RR, we conducted performance evaluations using a uniform flow cell under conditions of 20 ml / min of 1M KOH electrolyte driven by an electric peristaltic pump and a CO2 gas velocity of 30 ml / min. The specific sample preparation steps are as follows: 2 mg of sample was mixed with 150 μL of deionized water and 50 μL of 1 wt% Nafion solution and sonicated for 60 min. The above-mentioned ultra-uniform ink was then sprayed onto a gas diffusion layer of a pre-cut 1.5 cm × 1.5 cm carbon cloth using an electric spray gun, with a sample loading of 1 mg / cm³. -2 The working electrode was obtained by drying the film at room temperature. In addition, a calomel electrode and nickel foam were used as the reference electrode and counter electrode, respectively.

[0080] Figure 7The linear voltammetry curves show that the ECO2RR activity of Example 1 is significantly better than that of Comparative Example 1, exhibiting a lower onset potential and a larger current density.

[0081] Figure 8 The comparison of the advantageous products and their Faradaic efficiencies of different catalysts for ECO2RR shows that Example 1 can not only generate ethanol, a C2 product with high economic added value, but also has a high Faradaic efficiency. This indicates that Example 1 has a greater advantage in product variety compared to Comparative Example 1, Comparative Example 2 and other copper-based catalysts, and exhibits better conversion selectivity.

[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Therefore, any modifications made without departing from the overall concept of the present invention should be included within the protection scope of the present invention.

Claims

1. The application of trinuclear copper cluster atomic-level catalysts in electrocatalytic carbon dioxide reduction, characterized by: The trinuclear copper cluster atomic-level catalyst disperses atomic-level copper ions and non-metallic nitrogen atoms on a graphene-based support, and the copper ions are coordinated with carbon and nitrogen atoms through stable valence bonds to form a special trinuclear copper cluster structure. The catalyst contains 0.1–10.0 wt.% copper and 0.1–20.0 wt.% nitrogen. The heterogeneity and coordination effect between triatomic copper and carbon-nitrogen support can optimize the electronic state density between active copper sites, making them charge-rich centers that can adsorb and activate CO2 molecules. The trinuclear copper cluster atomic catalyst can achieve highly selective conversion of CO2 molecules into high-value-added C2 product ethanol, achieving a high-efficiency electrocatalytic reduction of CO2 with a Faraday efficiency of over 70%. The preparation steps of the catalyst are as follows: 1) Preparation of Cu3-NF precursor: Add 0.35 g CuCl2·2H2O to 50 mL of deionized water and stir well to prepare solution A. Add 0.15 g 1,2,4-triazole to 10 mL of deionized water and stir well to prepare solution B. Mix solution A and solution B to precipitate powdery crystals (Cu3-NF). 2) Weigh a certain amount of Cu3-NF precursor and 100 mg of graphene oxide and add them to a 100 mL beaker. Then add 80 mL of distilled water to the beaker. After adding a magnetic ball to the beaker, stir for 10 min and sonicate for 60 min to mix them thoroughly into a uniform suspension. 3) Transfer the suspension to a 250 mL rotary evaporator flask, and then use a rotary evaporator to evaporate the suspension under a high vacuum condition of 50~80℃ to remove the water solvent; 4) Scrape all the black solid residue from the rotary evaporation flask and collect it in an agate mortar, then grind it thoroughly to obtain a black powder material (Cu3-NF-GO). 5) The Cu3-NF-GO material was placed in a fast-moving boat and calcined in seconds at an ultra-fast temperature of 700~2000 ℃ under inert nitrogen protection. After pyrolysis for 5 seconds, the trinuclear copper cluster atomic-level catalyst Cu3-NG was obtained.

2. The application according to claim 1, characterized in that: In step 2), a certain amount of Cu3-NF precursor and 100 mg of graphene oxide are weighed out. In parallel experiments, 2 mg, 6 mg, 12 mg, 18 mg or 25 mg of Cu3-NF precursor are weighed out respectively to control the copper atom loading of Cu3-NF-GO.

3. The application according to claim 1, characterized in that: In step 5), the entire calcination process of the black Cu3-NF-GO powder must be carried out under the protection of inert nitrogen gas to avoid the formation of unfavorable oxides.

4. The application according to claim 1, characterized in that: In step 5), the black Cu3-NF-GO powder needs to be heated to 700~2000 ℃ with the assistance of a fast-moving boat, and after pyrolysis is completed in 5 s, it is then rapidly cooled to room temperature in an inert atmosphere.

5. The application according to claim 1, characterized in that: In a gas diffusion flow electrolytic cell divided into a cathode cell and an anode cell by a proton exchange membrane, a calomel electrode and nickel foam are used as the reference electrode and the counter electrode, respectively, and a carbon cloth coated with Cu3-NG on the gas diffusion layer is used as the working electrode to produce ethanol from carbon dioxide under constant current. An electric peristaltic pump is used to circulate and transport the cathode and anode electrolytes. In this process, Cu3-NG is sprayed onto the gas diffusion layer of carbon cloth using a spray gun, with a loading of 0.1~5 mg cm⁻¹. -2 .

6. The application according to claim 5, characterized in that: The constant current range mentioned above is 50 ~ 2000 mA cm⁻¹ -2 ; The electrolyte is potassium hydroxide with a concentration of 0.1~1.0 M, and the electrolyte flow rate driven by the electric peristaltic pump is 10~100 ml / min; the carbon dioxide gas rate is 10~100 ml / min. The dimensions of the carbon cloth with the gas diffusion layer are 1.0 cm × 1.0 cm to 10.0 cm × 10.0 cm.

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