Green and high-activity method for preparing formate by reducing carbon dioxide through electro-catalysis

Abstract

The invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and particularly relates to a green and high-activity method for preparing formate through electrocatalytic carbon dioxide reduction. Comprising the following steps: loading a cathode catalyst on cathode carbon paper to obtain a catalytic cathode; loading an anode catalyst on the anode titanium felt to obtain a catalytic anode; constructing a flowing electrolytic tank by utilizing the catalytic cathode and the catalytic anode; carbon dioxide gas is introduced into the gas flow channel, so that the carbon dioxide gas is diffused to the catalytic cathode; an alkaline electrolyte is introduced into the liquid flow channel, so that the alkaline electrolyte flows through the catalytic anode; and voltage is applied to the flowing electrolytic tank for an electrolytic reaction, a product of the catalytic anode is collected, and formate is obtained after concentration and distillation. The method disclosed by the invention can be operated for a long time under the current density of 500-600mA / cm < 2 >, and the formate content in the formate solution can reach about 13%.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and in particular relates to a green and highly active method for preparing formate by electrocatalytic carbon dioxide reduction. Background Art

[0002] With the acceleration of global industrialization, carbon dioxide emissions continue to increase, leading to serious greenhouse effects and environmental problems. How to effectively utilize carbon dioxide resources and convert them into high-value-added chemicals has become a hot topic in current research. Electrocatalytic carbon dioxide reduction technology is considered a promising carbon dioxide conversion pathway due to its mild reaction conditions, simple operation, and ability to be driven by renewable energy. Among the many carbon dioxide reduction products, formate has attracted much attention due to its wide application in chemical, pharmaceutical, and energy fields.

[0003] Conventional electrocatalytic carbon dioxide reduction to formate production primarily utilizes homogeneous electrolytic cell systems, which suffer from low current density, poor product selectivity, and low energy efficiency. While flow electrolytic cells have gained attention in recent years for their ability to operate at high current densities, existing technologies still face challenges such as insufficient catalyst activity and difficulty separating products. In particular, during the cathode reaction, key challenges remain: improving the mass transfer efficiency of carbon dioxide and maintaining a stable three-phase interface, as well as effectively controlling the impact of the anodic oxidation reaction on product selectivity.

[0004] Single-metal catalysts used in existing technologies often suffer from drawbacks such as high overpotential and poor stability, while conventional electrolytic cell designs struggle to simultaneously optimize gas diffusion and ion transport efficiency. Furthermore, hydroxide ions generated at the cathode during the reaction migrate to the anode, where they neutralize protons. This not only reduces electrolyte utilization but can also cause pH fluctuations, impacting reaction stability. Summary of the Invention

[0005] To solve the problems in the prior art, the present invention provides a green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide to produce formate. 2 It can run for a long time at a low current density, and the formate content in the formate solution can reach about 13%.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a green and highly active method for preparing formate by electrocatalytic reduction of carbon dioxide, comprising the following steps: Loading cathode catalyst on cathode carbon paper to obtain catalytic cathode; loading the anode catalyst on the anode titanium felt to obtain a catalytic anode; The catalytic cathode and catalytic anode are used to construct a flow electrolysis cell. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, the catalytic cathode, a cation exchange membrane, a solid resin particle layer, the catalytic anode, and an anode plate. The cathode plate is provided with a gas flow channel, and the anode plate is provided with a liquid flow channel. Introducing carbon dioxide gas into the gas flow channel so that the carbon dioxide gas diffuses into the catalytic cathode; introducing alkaline electrolyte into the liquid flow channel so that the alkaline electrolyte flows through the catalytic anode; A voltage is applied to the flow electrolysis cell to carry out an electrolysis reaction, and the product of the catalytic anode is collected and concentrated and distilled to obtain formate.

[0007] Preferably, the cathode catalyst is one or more of a bismuth-indium bimetallic catalyst, a bismuth-tin bimetallic catalyst and a tin-indium bimetallic catalyst.

[0008] Preferably, the anode catalyst is iridium oxide.

[0009] Preferably, the solid resin particles are one or more of Dowex 50WX8 cation exchange resin, D001H hydrogen-type macroporous strongly acidic cation exchange resin and 001X8 powder ball cation exchange resin.

[0010] Preferably, the thickness of the cation exchange membrane is 20 μm, 40 μm, 80 μm or 100 μm.

[0011] Preferably, the alkaline electrolyte is one or more of potassium hydroxide electrolyte and sodium hydroxide electrolyte.

[0012] Preferably, the concentration of the alkaline electrolyte is 0.1-0.5 mol / L; the flow rate of the alkaline electrolyte is 1-5 mL / min.

[0013] Preferably, the reduction potential of the cathode plate ranges from -5V to -1V.

[0014] Preferably, the flow rate of the carbon dioxide gas is 50-100 mL / h.

[0015] Preferably, polytetrafluoroethylene gaskets are provided between the cathode plate and the catalytic cathode, between the catalytic cathode and the cation exchange membrane, between the cation exchange membrane and the solid resin particle layer, between the solid resin particle layer and the catalytic anode, and between the catalytic anode and the anode plate.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a green, efficient and sustainable method for preparing formate by electrocatalytic reduction of carbon dioxide, which has significant environmental and economic advantages: by loading the cathode catalyst on highly conductive carbon paper, the reaction interface is effectively enlarged and the electron transfer path is optimized, which significantly improves the selectivity and current density of CO2 reduction to formate, inhibits side reactions such as hydrogen evolution, and significantly improves the product yield. By passing an alkaline electrolyte, the reaction can be carried out at 500-600 mA / cm 2 It can run for a long time at a low current density, and the formate content can reach about 13%; at the same time, the solid resin particle layer can further enhance ion conduction and reduce ohmic loss; the use of the cation exchange membrane effectively prevents the migration of cathode by-products and ensures the purity of the anode product. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0018] Figure 1 Current density diagram for the electrocatalytic reduction of carbon dioxide to prepare formate in different media; Figure 2 Graph showing formate concentrations at different alkaline electrolyte concentrations in Examples 1 to 5 of the present invention. DETAILED DESCRIPTION

[0019] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0020] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0021] All features, such as values, amounts, contents, and concentrations, described herein as numerical ranges or percentage ranges are provided for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0022] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0023] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0024] The present invention is described in further detail below with reference to the accompanying drawings: The present invention provides a green and highly active method for preparing formate by electrocatalytic reduction of carbon dioxide, comprising the following steps: Loading cathode catalyst on cathode carbon paper to obtain catalytic cathode; loading the anode catalyst on the anode titanium felt to obtain a catalytic anode; A flow electrolysis cell is constructed using a catalytic cathode and a catalytic anode. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, a catalytic cathode, a cation exchange membrane, a solid resin particle layer, a catalytic anode, and an anode plate. The cathode plate is provided with a gas flow channel, and the anode plate is provided with a liquid flow channel. High-purity carbon dioxide gas at a flow rate of 50-100 mL / h is introduced into the gas flow channel to diffuse the carbon dioxide gas to the catalytic cathode; an alkaline electrolyte at a flow rate of 1-5 mL / min and a concentration of 0.1-0.5 mol / L is introduced into the liquid flow channel to flow through the catalytic anode; Turn on the electrochemical workstation polarization potential test, set the cathode plate reduction potential range to -5V~-1V, test the current density, and apply voltage to the flow electrolytic cell to perform the electrolysis reaction. Collect the product at the catalytic anode - formate solution. After concentration and distillation, the formate solution can be obtained to obtain high-purity formate.

[0025] The present invention effectively enlarges the reaction interface and optimizes the electron transfer path by loading the cathode catalyst on highly conductive carbon paper, significantly improving the selectivity and current density of CO2 reduction to formate, inhibiting side reactions such as hydrogen evolution, and significantly improving the product yield. The flow electrolysis cell adopts a separation design of the cathode gas flow channel and the anode liquid flow channel, combined with a cation exchange membrane and a solid resin particle layer to achieve efficient mass transfer and ion selective migration at the gas-liquid-solid three-phase interface, while also blocking direct contact between the cathode CO2 and the anode electrolyte, avoiding cross contamination and improving reaction stability. The circulating flow of the alkaline electrolyte not only promotes the anode reaction kinetics, but also balances mass transfer and reaction rate by adjusting the flow rate, with high reaction sensitivity and high reaction rate; the continuous introduction of cathode CO2 gas ensures an adequate supply of reactants, and the two work together to reduce concentration polarization and reduce energy consumption. At the same time, the solid resin particle layer can further enhance ion conduction and reduce ohmic loss; the use of the cation exchange membrane effectively prevents the migration of cathode byproducts and ensures the purity of the anode product.

[0026] The present invention provides a green, efficient, and sustainable method for preparing formate by electrocatalytic carbon dioxide reduction, which has significant environmental and economic advantages. On the one hand, carbon dioxide is consumed during the electrocatalytic carbon dioxide reduction process, and the surplus carbon dioxide can be converted into low-carbon, high-value-added chemical products through electrocatalytic reduction, thereby reducing consumption and increasing efficiency, thereby improving its industrial application value. On the other hand, the electrocatalytic reduction preparation process can operate continuously and stably for a long time at room temperature and pressure, generates few by-products, and has a simple and efficient purification process. It is an economical, environmentally friendly, and efficient method for preparing formate. In addition, by selecting a catalyst with high selectivity and high activity to be loaded on the electrode material, the selectivity and reaction activity of carbon dioxide to formate are greatly improved.

[0027] The method for loading the cathode catalyst onto cathode carbon paper involves spraying the cathode catalyst evenly onto the cathode carbon paper. The method for loading the anode catalyst onto anode titanium felt involves spraying the cathode catalyst evenly onto the cathode carbon paper. For loading the cathode catalyst onto cathode carbon paper, the spraying process enables a uniform distribution and controllable thickness of the catalyst layer, ensuring full exposure of the active sites. For loading the anode catalyst onto anode titanium felt, the spraying method adapts to the three-dimensional porous structure of the titanium felt, allowing the catalyst to form close contact with the conductive substrate.

[0028] The cathode catalyst is one or more of a bismuth-indium bimetallic catalyst, a bismuth-tin bimetallic catalyst, and a tin-indium bimetallic catalyst. Bimetallic catalysts, through electronic synergy between the metal components, can effectively regulate the adsorption and activation of carbon dioxide molecules, significantly improving the selectivity of formate formation.

[0029] The anode catalyst is iridium oxide, whose unique crystal structure and abundant oxygen vacancy defects provide a large number of highly efficient active sites for the water oxidation reaction. Furthermore, the oxyhydroxide layer formed on its surface significantly reduces the reaction energy barrier and promotes the proton-electron transfer process. Its excellent corrosion resistance effectively resists anodic polarization corrosion at high potentials.

[0030] The solid resin particles are one or more of Dowex 50WX8 cation exchange resin, D001H hydrogen-form macroporous strongly acidic cation exchange resin, and 001X8 powdered sphere cation exchange resin. The strong acidity of the resin particles maintains a stable reaction environment, while their excellent mechanical strength and chemical stability ensure the system's reliability during long-term operation, providing an ideal ion-conducting medium for the carbon dioxide electroreduction process.

[0031] Cation exchange membranes are available in thicknesses of 20μm, 40μm, 80μm, or 100μm, adapting to different membrane material systems for different electrolysis conditions. Thinner membranes (20-40μm) significantly reduce proton transport resistance and improve current efficiency, while thicker membranes (80-100μm) exhibit excellent mechanical strength and dimensional stability, effectively suppressing membrane swelling.

[0032] The alkaline electrolyte is one or more of potassium hydroxide electrolyte and sodium hydroxide electrolyte. These two strong alkaline electrolytes can provide a stable high pH environment, effectively promote the activation process of carbon dioxide on the cathode surface, and inhibit the occurrence of competitive hydrogen evolution side reaction. Figure 1 As shown in the figure, the current density of different liquids is significantly different, and the current density of alkaline electrolyte medium is significantly higher. Among them, the current density of ultrapure water medium is 95~100mA / cm 2 , the current density under alkaline electrolyte medium is 500~600mA / cm 2 In comparison, the current density of alkaline electrolyte medium is significantly better than that of ultrapure water medium. At the same time, the alkaline electrolyte can be used at 500~600mA / cm 2 Long-term operation at high current density.

[0033] Polytetrafluoroethylene gaskets are installed between the cathode plate and the catalytic cathode, between the catalytic cathode and the cation exchange membrane, between the cation exchange membrane and the solid resin particle layer, between the solid resin particle layer and the catalytic anode, and between the catalytic anode and the anode plate, and are secured in place by bolts. The gaskets' elastic compensation function mitigates structural deformation caused by thermal expansion and mechanical stress, while the bolted fastening provides adjustable sealing pressure, ensuring gas-liquid sealing while preventing component damage caused by overload.

[0034] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0035] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0036] Example 1 The prepared bismuth-indium bimetallic catalyst is evenly sprayed on the cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolysis cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, a catalytic cathode, a 20 μm cation exchange membrane, Dowex 50WX8 cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, potassium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.1 mol / L and an electrolyte flow rate of 1 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 50 mL / h; the reduction potential of the electrochemical workstation was set to -1 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0037] Example 2 The prepared bismuth-tin bimetallic catalyst is evenly sprayed on the cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolytic cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolytic cell comprises, from the cathode plate to the anode plate, a catalytic cathode, a 40 μm cation exchange membrane, a D001H hydrogen-type macroporous strongly acidic cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, sodium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.2 mol / L and an electrolyte flow rate of 2 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 60 mL / h; the reduction potential of the electrochemical workstation was set to -2 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0038] Example 3 The prepared tin-indium bimetallic catalyst is evenly sprayed on the cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolytic cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolytic cell comprises, from the cathode plate to the anode plate, a cathode plate, a catalytic cathode, a 60 μm cation exchange membrane, 001X8 powder ball cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, potassium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.3 mol / L and an electrolyte flow rate of 3 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 70 mL / h; the reduction potential of the electrochemical workstation was set to -3 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0039] Example 4 The prepared bismuth-indium bimetallic catalyst is evenly sprayed on the cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolysis cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, an 80 μm cation exchange membrane, Dowex 50WX8 cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, sodium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.4 mol / L and an electrolyte flow rate of 4 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 80 mL / h; the reduction potential of the electrochemical workstation was set to -4 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0040] Example 5 The prepared bismuth-indium bimetallic catalyst is evenly sprayed on the cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolysis cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, a catalytic cathode, a 100 μm cation exchange membrane, Dowex 50WX8 cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, potassium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.5 mol / L and an electrolyte flow rate of 5 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 90 mL / h; the reduction potential of the electrochemical workstation was set to -5 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0041] Example 6 The prepared bismuth-indium bimetallic catalyst and bismuth-tin bimetallic catalyst are evenly sprayed on cathode carbon paper to obtain a catalytic cathode; The prepared indium oxide is evenly sprayed on the anode titanium felt to obtain a catalytic anode; A flow electrolytic cell is assembled using a catalytic cathode and a catalytic anode. The flow electrolytic cell comprises, from the cathode plate to the anode plate, a catalytic cathode, a 100 μm cation exchange membrane, a mixture of Dowex 50WX8 cation exchange resin and 001X8 powder ball cation exchange resin, a catalytic anode, and an anode plate. Adjacent components are separated by polytetrafluoroethylene gaskets and fixed in place by bolts. The assembled flow electrolytic cell was connected to an electrochemical workstation, the electrodes were connected, potassium hydroxide electrolyte was introduced into the anode with an electrolyte concentration of 0.5 mol / L and an electrolyte flow rate of 5 mL / min, and high-purity carbon dioxide gas was introduced into the cathode with a flow rate of 100 mL / h; the reduction potential of the electrochemical workstation was set to -5 V, constant voltage polarization was started to generate current density, and the product at the catalytic anode - formate solution - was collected. The formate solution was concentrated and distilled to obtain high-purity formate.

[0042] like Figure 2As shown, the formate concentration under different alkaline electrolyte concentrations varies significantly. As the alkaline electrolyte concentration increases, the formate concentration shows a trend of first increasing and then decreasing, reaching a maximum of 12.8 mg / L. The formate content in the formate solution can reach approximately 13%. The electrocatalytic carbon dioxide reduction technology for preparing formate of the present invention is not only safe, environmentally friendly, and economical, but also can achieve stable and rapid preparation of formate, and has great application prospects in the field of electrocatalytic carbon dioxide reduction.

[0043] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A green and highly active method for preparing formate by electrocatalytic reduction of carbon dioxide, characterized in that: The following steps are involved: Loading cathode catalyst on cathode carbon paper to obtain catalytic cathode; loading the anode catalyst on the anode titanium felt to obtain a catalytic anode; The catalytic cathode and catalytic anode are used to construct a flow electrolysis cell. The flow electrolysis cell comprises, from the cathode plate to the anode plate, a cathode plate, the catalytic cathode, a cation exchange membrane, a solid resin particle layer, the catalytic anode, and an anode plate. The cathode plate is provided with a gas flow channel, and the anode plate is provided with a liquid flow channel. Introducing carbon dioxide gas into the gas flow channel so that the carbon dioxide gas diffuses into the catalytic cathode; introducing alkaline electrolyte into the liquid flow channel so that the alkaline electrolyte flows through the catalytic anode; A voltage is applied to the flow electrolysis cell to carry out an electrolysis reaction, and the product of the catalytic anode is collected and concentrated and distilled to obtain formate.

2. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The cathode catalyst is one or more of a bismuth-indium bimetallic catalyst, a bismuth-tin bimetallic catalyst, and a tin-indium bimetallic catalyst.

3. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The anode catalyst is iridium oxide.

4. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The solid resin particles are one or more of Dowex 50WX8 cation exchange resin, D001H hydrogen-type macroporous strongly acidic cation exchange resin and 001X8 powder ball cation exchange resin.

5. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The thickness of the cation exchange membrane is 20 μm, 40 μm, 80 μm or 100 μm.

6. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The alkaline electrolyte is one or more of potassium hydroxide electrolyte and sodium hydroxide electrolyte.

7. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The concentration of the alkaline electrolyte is 0.1-0.5 mol / L; the flow rate of the alkaline electrolyte is 1-5 mL / min.

8. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The reduction potential range of the cathode plate is -5V~-1V.

9. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: The flow rate of the carbon dioxide gas is 50-100 mL / h.

10. The green and highly active electrocatalytic method for preparing formate by reducing carbon dioxide according to claim 1, characterized in that: Polytetrafluoroethylene gaskets are provided between the cathode plate and the catalytic cathode, between the catalytic cathode and the cation exchange membrane, between the cation exchange membrane and the solid resin particle layer, between the solid resin particle layer and the catalytic anode, and between the catalytic anode and the anode plate.

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