A method for preparing and applying a lead-doped copper-based electrocatalyst

Abstract

This invention discloses a method for preparing and applying a lead-doped copper-based electrocatalyst. The method includes the following steps: mixing an aqueous solution containing trisodium citrate dihydrate with an aqueous solution containing copper sulfate, then adding an aqueous solution of sodium hydroxide to obtain an orange precursor; dissolving the dried orange precursor in a methanol solution of lead nitrate to anchor Pb nanoparticles onto a copper substrate (PbCu2O); and finally pyrolyzing the PbCu2O in a tube furnace to obtain the lead-doped copper-based electrocatalyst. The electrocatalyst for the reduction of carbon monoxide to multi-carbon products obtained by this invention exhibits a Faradaic efficiency of 96.5%, with a Faradaic efficiency of 66.5% for ethanol, and a cycling stability of 100 h.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic carbon monoxide reduction catalyst technology, specifically relating to a lead-doped copper-based electrocatalyst and its preparation method. Background Technology

[0002] Carbon monoxide (CMO) is an important carbon-containing molecule with wide applications in chemical synthesis, energy conversion, and carbon resource recycling. Currently, industrially, CMO is mainly produced from fossil resources such as coal and natural gas through reforming, partial oxidation, or gasification processes. These processes typically involve high energy consumption, complex processes, and significant carbon dioxide emissions, hindering green and low-carbon development. Therefore, it is necessary to explore more environmentally friendly, efficient, and sustainable methods for CMO conversion and utilization. In recent years, electrocatalysis technology, driven by renewable energy power generation, has shown great application potential in the field of small molecule conversion. Among these, the electrocatalytic reduction of CMO can convert CMO into high-value-added fuels or chemicals such as methane, ethylene, and ethanol under relatively mild conditions, providing a new technological approach for the high-value utilization of carbon resources. Simultaneously, as a key C1 intermediate, the moderate molecular structure and reactivity of CMO help lower the reaction energy barrier in the formation of multi-carbon products, improving the slow reaction kinetics and poor product selectivity problems present in the direct reduction of carbon dioxide.

[0003] Because the electrocatalytic reduction of carbon monoxide involves complex processes such as adsorption of *CO intermediates, CC coupling, and multi-step proton-electron transfer, the design of the electrocatalyst directly determines the selectivity of the target product and the reaction rate. Currently, technologies for preparing electrocatalysts for the electrocatalytic reduction of carbon monoxide have been reported. Patent CN115491699B discloses a nano-copper-based catalyst, its preparation method, and its application in the electrocatalytic reduction of carbon dioxide and carbon monoxide. The Faradaic efficiency for multi-carbon products reaches up to 95%, but the single-product selectivity is poor, affecting the further practical application of the catalyst. Patent CN118547321A discloses a method for preparing a catalyst for the electrocatalytic reduction of carbon monoxide to produce C2 and higher products, and its application. Although this catalyst achieves a Faradaic efficiency of 96.3% for C2 and higher products, the products are still predominantly multiple C2 and higher products coexisting, and the selectivity for a single target product still needs improvement, severely restricting its further practical application. Summary of the Invention

[0004] The purpose of this invention is to address the limitations of current technologies by providing a method for preparing and applying a lead-doped copper-based electrocatalyst. This method uses cuprous oxide cubes as a precursor and employs an ion exchange strategy under room-temperature vacuum conditions to allow Pb species to enter the interior of the Cu₂O lattice, rather than merely remaining on the surface as deposits or forming independent particles. Subsequent heat treatment forms a Pb-Cu₂O catalyst with stable lattice-doped characteristics. This simultaneously promotes the carbon-carbon coupling step in the electrocatalytic carbon monoxide reduction reaction. The electrocatalytic carbon monoxide reduction to multi-carbon products obtained by this invention exhibits a Faradaic efficiency of 96.5%, with a Faradaic efficiency of 66.5% for ethanol and a cycling stability of 100 hours, achieving both high Faradaic efficiency and high cycling stability. This provides a new approach for green, efficient, and sustainable ethanol synthesis.

[0005] The technical solution of the present invention is as follows: A method for preparing a lead-doped copper-based electrocatalyst, the method comprising the following steps: (1) Mix the aqueous solution containing trisodium citrate dihydrate with the aqueous solution containing copper sulfate, add the aqueous solution of sodium hydroxide and stir for 5-10 minutes, then add the aqueous solution of ascorbic acid and stir for 10-30 minutes, then let stand for 30-90 minutes, and then centrifuge, wash and vacuum dry to obtain the orange precursor, namely Cu2O. The mass ratio of trisodium citrate dihydrate to copper sulfate is 1:0.5~2; for every 500~550mg of trisodium citrate dihydrate aqueous solution, add 2~10 ml of sodium hydroxide aqueous solution and 2~10 ml of ascorbic acid aqueous solution. The concentration of the sodium hydroxide aqueous solution is 1~5 mol / L; the concentration of the ascorbic acid aqueous solution is 1~5 mol / L; (2) The dried orange precursor was dissolved in a methanol solution of lead nitrate, and the mixture was vacuumed and stirred at room temperature for 12-15 hours to obtain an orange-yellow powder, i.e. Pb nanoparticles anchored on a copper substrate (Pb Cu2O). The mass ratio of the orange precursor to lead nitrate is 1:0.2~1; (3) PbCu2O is placed in the middle of a tube furnace and pyrolyzed at 200-300°C under an argon gas atmosphere and held for 1-3 hours to obtain lead-doped copper-based electrocatalyst.

[0006] The heating rate is 1~5℃ / min.

[0007] In the aqueous solution of trisodium citrate dihydrate, 500-550 mg of trisodium citrate dihydrate is added for every 800 mL of deionized water. In the aqueous solution of copper sulfate, 200-300 mg of copper sulfate is added to every 2 mL of deionized water.

[0008] The lead-doped copper-based electrocatalyst prepared by the method is used for the electrocatalytic reduction of carbon monoxide to generate multi-carbon products.

[0009] Specifically, the steps include: in a three-electrode system, the electrolytic cell through which carbon monoxide gas is passed is electrolyzed for 1 to 2 hours using a constant current method to obtain multi-carbon products; In the three-electrode system, an iridium-titanium mesh, Ag / AgCl, and carbon paper supported on a lead-doped copper-based electrocatalyst serve as the counter electrode, reference electrode, and working electrode, respectively; the electrolytic cell type is a flow cell electrolytic cell, and the diaphragm is a fumasep FAB-PK-130 membrane; the electrolyte composition is a solution containing 0.5~1M KOH; and the CO gas purity is 98%~100%. In the working electrode, 0.5~1mg of catalyst is loaded per 1 square centimeter of carbon paper; The electrolysis current range is -100mA to -400mA.

[0010] The essential features of this invention are: This invention constructs a Cu₂O catalyst with a stable doped structure by introducing Pb into the Cu₂O lattice using a room-temperature vacuum ion exchange strategy, followed by heat treatment. Unlike traditional surface deposition or simple composite methods, in this invention, Pb enters the Cu₂O lattice through ion exchange, which synergistically modulates the catalyst's crystal structure, local electronic properties, and surface reaction pathways. This optimizes CO adsorption, CC coupling, and subsequent hydrogenation of oxygen-containing intermediates, making the electrocatalytic carbon monoxide reduction reaction more favorable for the formation of liquid multi-carbon products such as ethanol, and reducing the occurrence of other competing side reactions. Therefore, the lead-doped copper-based catalyst prepared in this invention can effectively improve the selectivity and yield of liquid multi-carbon products, especially ethanol, in the electrocatalytic carbon monoxide reduction reaction.

[0011] The present invention has the following beneficial effects: 1. This invention achieves lead doping into the cuprous oxide cubic lattice through ion exchange. The preparation process is mild and simple to operate, and can effectively control the catalyst composition and local electronic structure while maintaining the original morphology and structure of the cuprous oxide cubic lattice.

[0012] 2. By constructing a lead-doped cuprous oxide cubic catalytic structure, this invention effectively regulates the adsorption of key reaction intermediates, CC coupling, and subsequent hydrogenation steps in the electrocatalytic carbon monoxide reduction process, thereby facilitating the generation of liquid multi-carbon products such as ethanol and improving the Faraday efficiency of multi-carbon products and ethanol.

[0013] 3. Since lead is doped into the lattice of cuprous oxide cube through ion exchange, it changes the electronic environment around the copper active sites and the adsorption behavior of reaction intermediates, thereby modulating the electrocatalytic carbon monoxide reduction reaction pathway. The pathway that was originally more likely to generate gaseous products is changed to a pathway that is more conducive to the generation of liquid multi-carbon products, thus effectively improving the electrocatalytic reduction performance of liquid multi-carbon products such as ethanol.

[0014] 4. After lead doping is incorporated into the cuprous oxide cubic lattice, it can optimize the adsorption and conversion process of key intermediates by the catalyst, promote the further hydrogenation of oxygen-containing intermediates after CC coupling, and inhibit the occurrence of competitive side reactions, thereby improving the selectivity of the formation of liquid multi-carbon products such as ethanol.

[0015] 5. Thanks to the reaction pathway regulation effect caused by lead doping, the lead-doped copper-based electrocatalyst prepared in this invention exhibits excellent catalytic performance in the electrocatalytic reduction of carbon monoxide. The Faradaic efficiency of the multi-carbon product can reach 96.5%, and the Faradaic efficiency of ethanol can reach 66.5%. It also has a cycle stability of up to 100 h, showing good prospects for practical application. Attached Figure Description

[0016] Figure 1 The image shows a scanning electron microscope image of the electrocatalyst prepared in Example 1.

[0017] Figure 2 The image shows a transmission electron microscope image of the electrocatalyst prepared in Example 1.

[0018] Figure 3 X-ray diffraction patterns of the electrocatalysts prepared in Examples 1, 2, and 3.

[0019] Figure 4 Linear sweep voltammetry curves of the electrocatalysts prepared in Examples 1, 2, and 3 in the electrolyte.

[0020] Figure 5 The image shows the Faraday efficiency of the electrocatalysts prepared in Examples 1 and 2.

[0021] Figure 6 The diagram shows the Faraday efficiency of the electrocatalysts prepared in Examples 1 and 3.

[0022] Figure 7 The image shows the cyclic stability of the electrocatalyst prepared in Example 1. Detailed Implementation

[0023] The specific implementation steps and accompanying drawings of the present invention will be described in full and clearly below. It should be noted that the specific implementation of the present invention should not be considered limited to these descriptions. For those skilled in the art, other embodiments or inferences obtained without innovation should be considered to fall within the scope of protection of the present invention.

[0024] Example 1: The specific preparation method of lead-doped copper-based electrocatalysts is as follows: (1) Dissolve 529 mg of trisodium citrate dihydrate (Na3C6H5O7·2H2O) in 800 mL of deionized water and sonicate for 5 minutes to obtain an aqueous solution containing Na3C6H5O7·2H2O.

[0025] (2) Dissolve 300 mg of copper sulfate in 2 mL of deionized water and sonicate for 5 minutes to obtain an aqueous solution containing copper sulfate.

[0026] (3) Mix all the aqueous solutions containing Na3C6H5O7·2H2O obtained above with the aqueous solution of copper sulfate and stir for 5 minutes to obtain the first mixed solution; (4) Dissolve 0.0024 mol of sodium hydroxide in 2 mL of deionized water and sonicate for 5 minutes to obtain an aqueous solution containing sodium hydroxide.

[0027] (5) Mix the first mixed solution with 2 mL of sodium hydroxide aqueous solution and stir for 5 minutes to obtain the second mixed solution.

[0028] (6) Dissolve 0.0024 mol of ascorbic acid in 2 mL of deionized water and sonicate for 5 minutes to obtain an aqueous solution containing ascorbic acid.

[0029] (7) Mix the second mixed solution with 2 mL of ascorbic acid aqueous solution and stir for 30 minutes. Let it stand for 1 hour to age. Then centrifuge, wash and vacuum dry to obtain the orange precursor, Cu2O.

[0030] (8) Dissolve 33.1 mg of lead nitrate in 50 mL of anhydrous methanol and sonicate for 60 minutes to obtain a methanol solution containing lead nitrate.

[0031] (9) Take 143 mg of dried Cu2O precursor and dissolve it in the methanol solution of lead nitrate obtained in the previous step. The solution is then vacuumed and stirred at room temperature for 12 hours to obtain an orange-yellow powder, i.e., Pb nanoparticles anchored on a copper substrate (PbCu2O). (10) Pb Cu2O was placed in the middle of a tube furnace and pyrolyzed at 200°C under an argon gas atmosphere at a rate of 5°C / min and held for 2 hours to obtain lead-doped copper-based electrocatalyst (Pb Cu2O).

[0032] The morphology of PbCu2O was observed using scanning electron microscopy (SEM). Figure 1 As shown, PbCu2O exhibits a smooth hexahedral structure, and no obvious lead nanoparticles were observed.

[0033] The morphology and structure of PbCu2O were analyzed using transmission electron microscopy (TEM). Figure 2 As shown, no aggregation of lead nanoparticles was observed even at high resolution, indicating that there was no excessive lead aggregation.

[0034] The phase composition of PbCu2O was analyzed using X-ray diffraction (XRD). Figure 3 As can be observed, the Pb-Cu2O samples all exhibit distinct diffraction peaks at approximately 29.6°, 36.4°, 42.3°, 61.3°, and 73.5°, corresponding to the (110), (111), (200), (220), and (211) crystal planes of Cu2O, respectively, which are in good agreement with the standard card Cu2O PDF#99-0041. This indicates that the lead-doped samples still maintain the main crystalline structure of Cu2O. Meanwhile, no characteristic diffraction peaks associated with metallic lead, lead oxide, or other impurities were observed in the figure, suggesting that the Pb species did not form an independent crystalline phase and is more likely to have entered the Cu2O cubic lattice as a dopant.

[0035] The electrocatalytic performance of PbCu2O was studied using linear sweep voltammetry. Figure 4 As shown, PbCu2O reaches -200 mA cm⁻¹ -2 The required potential correction at the same current density indicates that the introduction of Pb helps reduce the reaction overpotential and accelerate charge transfer kinetics. This demonstrates that PbCu2O possesses excellent electrocatalytic activity, thus illustrating that tandem catalytic active sites are crucial for promoting the electrocatalytic reduction of carbon monoxide.

[0036] Specifically, the steps are as follows: (1) Electrolytic reduction of carbon monoxide was carried out on a CHI-1140D electrochemical workstation of Shanghai Chenhua using a three-electrode system, with an iridium-titanium mesh, Ag / AgCl, and an area of ​​1 cm². 2 The carbon paper-supported catalyst was used as the counter electrode, reference electrode, and working electrode, respectively. (2) The electrolysis test was carried out in a flow electrolytic cell separated by a fumasep FAB-PK-130 membrane, in which each anode and cathode contained 20 ml of 1 MKOH electrolyte, and the flow rate was controlled at 10 mL / min using a peristaltic pump. -1The circulating CO gas with a purity of 99.9999% was controlled by a flow meter to flow at a rate of 10 sccm (1 atm, 273.15K) and sent into the cathode chamber to provide the reaction gas. The pretreatment of the fumasep FAB-PK-130 membrane was first soaked in deionized water at room temperature for 24 hours. (3) The preparation steps of the working electrode are as follows: 10 mg of catalyst is dispersed in a mixed solution (50 μL Nafion solution + 950 μL anhydrous methanol) and ultrasonically treated for half an hour to form a uniform ink. 100 μL of catalyst ink is dropped into a 1 cm 2 (4) All electrolysis potentials involved in this work are reversible hydrogen electrode (RHE) potentials, and the conversion formula is E (RHE) = E (Ag / AgCl) + 0.059 × pH + 0.197. (5) The electrocatalyst was subjected to chronovoltammetry tests for 1 hour at different electrolysis potentials. The gaseous products were brought into the Fuli GC9790plus chromatograph for analysis. The electrolysis potential range was -100mA to -400mA. (6) After the chronovoltammetry test was completed, 1 mL of electrolyte was taken out and the liquid products synthesized by the electrocatalyst were qualitatively and quantitatively analyzed by 1H nuclear magnetic resonance spectroscopy.

[0037] The gaseous products and liquid products in the electrolyte after electrolysis of PbCu2O by chronovoltaic method were detected using a Fuli GC9790plus chromatograph and a 1H nuclear magnetic resonance spectrometer, respectively. Figure 5 and 6 As shown, the Faradaic efficiency of PbCu2O for multi-carbon products reaches 96.5% under an applied current of -200mA. Among them, the Faradaic efficiency of gaseous products ethylene is 19% and that of hydrogen is 3.6%. The Faradaic efficiency of multi-carbon products is 66.5% for ethanol, 5.4% for acetic acid and 5.6% for n-propanol. Figure 5 and 6 The PbCu2O, Cu2O, and SnCu2O involved were all tested using a three-electrode system on a CHI-1140D electrochemical workstation. The three-electrode system used an iridium-titanium mesh, Ag / AgCl, and a 1 cm² area. 2 1 mg of catalyst was loaded onto carbon paper and used as the counter electrode, reference electrode, and working electrode, respectively. The electrolysis test method employed was the chronovoltaic method. The applied current range was -100 mA to -400 mA (constant current). The electrolyte composition was 1 MKOH. The gaseous and liquid products after electrolysis were measured using a Fuli GC9790plus chromatograph and a 1H nuclear magnetic resonance spectrometer, respectively.

[0038] Long-term stability tests were conducted on PbCu2O using an applied current of -200 mA, such as... Figure 7 As shown, the voltage of the system experienced a brief and rapid adjustment at the beginning, then quickly stabilized and remained at a relatively constant level during 100 hours of continuous operation, demonstrating good electrochemical stability and mass transfer matching at this operating current. The Faraday efficiency of ethanol remained around 60% throughout the entire test period, without showing a significant decline over time, indicating that the ethanol formation selectivity of the catalyst can be stably maintained under long-term, high-current-density operation.

[0039] Example 2: The other steps are the same as in Example 1, except that steps (8) and (9) of Example 1 are omitted, and the resulting sample is cuprous oxide cube (Cu2O). The phase composition of Cu₂O was analyzed using X-ray diffraction patterns. For example... Figure 3 As shown, the samples all exhibited obvious diffraction peaks at approximately 29.6°, 36.4°, 42.3°, 61.3°, and 73.5°, corresponding to the (110), (111), (200), (220), and (211) crystal planes of Cu2O, respectively. This indicates the successful synthesis of cuprous oxide cubes.

[0040] The electrocatalytic performance of Cu₂O was analyzed using linear sweep voltammetry. For example... Figure 4 As shown, the current density of Cu2O at each potential is lower than that of PbCu2O, indicating that the electrocatalytic activity of Cu2O for carbon monoxide reduction is lower than that of PbCu2O.

[0041] The gaseous products and liquid products in the electrolyte after electrolysis of Cu₂O by chronovoltaic method were detected using a Fuli GC9790plus chromatograph and a 1H nuclear magnetic resonance spectrometer, respectively. Figure 5 As shown, the Faraday efficiency of Cu2O for ethanol is only 16.5% under an applied current of -200mA.

[0042] The Faraday efficiency of Cu2O at an applied current of -200 mA is only 16.5%, lower than that of PbCu2O. Due to the lack of lead doping, the copper-based catalyst lacks the local electronic structure regulation effect generated by lead entering the cuprous oxide cubic lattice through ion exchange. This makes it difficult to effectively optimize the adsorption and conversion behavior of key reaction intermediates, hindering the transformation of the electrocatalytic carbon monoxide reduction reaction into the formation pathway of liquid multi-carbon products such as ethanol. Consequently, this reduces the Faraday efficiency of liquid multi-carbon products and the overall performance of the catalyst.

[0043] Example 3: The other steps are the same as in Example 1, except that in steps (8) and (9) of Example 1, the lead nitrate methanol solution is replaced with tin chloride methanol solution to obtain tin-doped copper-based catalyst sample (Sn Cu2O).

[0044] The electrocatalytic performance of SnCu2O was analyzed using linear sweep voltammetry. Figure 4 As shown, the current density of SnCu2O at each potential is lower than that of PbCu2O, indicating that the electrocatalytic activity of SnCu2O for carbon monoxide reduction is lower than that of PbCu2O.

[0045] The gaseous products and liquid products in the electrolyte after electrolysis of SnCu2O by chronovoltaic method were detected using a Fuli GC9790plus chromatograph and a 1H nuclear magnetic resonance spectrometer, respectively. Figure 5 As shown, the Faraday efficiency of SnCu2O with an applied current of -200mA is only 17%.

[0046] The Faraday efficiency of SnCu2O in the electrocatalytic reduction of carbon monoxide to ethanol is only 17%, far lower than that of SnCu2O. Therefore, the reason for the performance degradation of SnCu2O in the examples is that Sn doping failed to effectively control the cuprous oxide lattice and reaction pathway, weakening the catalyst's stability of key oxygen-containing intermediates and its subsequent hydrogenation conversion ability, thereby limiting the conversion of reaction intermediates into liquid multi-carbon products such as ethanol.

[0047] Example 4: The other steps are the same as in Example 1, except that the mass of lead nitrate in step (8) of Example 1 is replaced by 71.5 mg instead of 33.1 mg; The resulting material properties are close; Example 5: The other steps are the same as in Example 1, except that the annealing temperature in step (10) of Example 1 is replaced by 300°C instead of 200°C; The resulting material properties are close; In summary, the electrocatalyst prepared in this invention solves the problem of existing electrocatalytic carbon monoxide reduction catalysts struggling to simultaneously achieve high multi-carbon product Faradaic efficiency, high ethanol selectivity, and long-term stability in the formation of liquid multi-carbon products. As a highly efficient electrocatalytic carbon monoxide reduction catalyst, the PbCu2O catalyst of this invention incorporates lead into the cubic lattice of cuprous oxide through ion exchange, thereby effectively controlling the local electronic structure and surface reaction pathways of the catalyst. This makes the electrocatalytic carbon monoxide reduction reaction more favorable for the formation of liquid multi-carbon products such as ethanol. Benefiting from the reaction pathway shift caused by lead doping and its promoting effect on the conversion of key oxygen-containing intermediates, PbCu2O exhibits both high multi-carbon product Faradaic efficiency and high ethanol Faradaic efficiency in the electrocatalytic carbon monoxide reduction reaction. The Faradaic efficiency for multi-carbon products reaches 96.5%, and the Faradaic efficiency for ethanol reaches 66.5%, with a long-term cycling stability of 100 h. This provides a new technical solution for the efficient electrocatalytic preparation of liquid multi-carbon products such as ethanol.

[0048] The above content is merely an example and illustration of the concept of the present invention. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention. Any modifications, alterations, and equivalent changes made by those skilled in the art based on the above-disclosed technical content without departing from the spirit and scope of the present invention are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the scope of the technical solution of the present invention.

[0049] Matters not covered in this invention are common knowledge.

Claims

1. A method for preparing a lead-doped copper-based electrocatalyst, characterized in that, The method includes the following steps: (1) Mix the aqueous solution containing trisodium citrate dihydrate with the aqueous solution containing copper sulfate, add the aqueous solution of sodium hydroxide and stir for 5-10 minutes, then add the aqueous solution of ascorbic acid and stir for 10-30 minutes, then let stand for 30-90 minutes, and then centrifuge, wash and vacuum dry to obtain the precursor, namely Cu2O. The mass ratio of trisodium citrate dihydrate to copper sulfate is 1:0.5~2; for every 500~550mg of trisodium citrate dihydrate aqueous solution, add 2~10 ml of sodium hydroxide aqueous solution and 2~10 ml of ascorbic acid aqueous solution. The concentration of the sodium hydroxide aqueous solution is 1~5 mol / L; the concentration of the ascorbic acid aqueous solution is 1~5 mol / L; (2) The dried orange precursor was dissolved in a methanol solution of lead nitrate, and the mixture was vacuumed and stirred at room temperature for 12-15 hours to obtain an orange-yellow powder, i.e. Pb nanoparticles anchored on a copper substrate (Pb Cu2O). The mass ratio of the orange precursor to lead nitrate is 1:0.2~1; (3) PbCu2O is placed in the middle of a tube furnace and pyrolyzed for 1 to 3 hours in an argon gas atmosphere at a temperature of 200 to 300°C to obtain lead-doped copper-based electrocatalyst.

2. The method for preparing the lead-doped copper-based electrocatalyst as described in claim 1, characterized in that, The heating rate in step (3) is 1~5℃ / min.

3. The method for preparing the lead-doped copper-based electrocatalyst as described in claim 1, characterized in that, In the aqueous solution of trisodium citrate dihydrate, 500-550 mg of trisodium citrate dihydrate is added for every 800 mL of deionized water.

4. The method for preparing the lead-doped copper-based electrocatalyst as described in claim 1, characterized in that, In the aqueous solution of copper sulfate, 200-300 mg of copper sulfate is added to every 2 mL of deionized water.

5. The application of the lead-doped copper-based electrocatalyst prepared by the method described in claim 1, characterized in that, It is used for the electrocatalytic reduction of carbon monoxide to produce multi-carbon products.

6. The application as described in claim 5, characterized in that, The process includes the following steps: In a three-electrode system, a constant current method is used to electrolyze an electrolytic cell through which carbon monoxide gas is passed for 1 to 2 hours to obtain a multi-carbon product; In the three-electrode system, an iridium-titanium mesh, Ag / AgCl, and carbon paper supported on a lead-doped copper-based electrocatalyst serve as the counter electrode, reference electrode, and working electrode, respectively; the electrolytic cell type is a flow cell electrolytic cell, and the diaphragm is a fumasep FAB-PK-130 membrane; the electrolyte composition is a solution containing 0.5~1M KOH; and the CO gas purity is 98%~100%. In the working electrode, 0.5~1mg of catalyst is loaded per 1 square centimeter of carbon paper; The electrolysis current range is -100mA to -400mA.

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