Polyester modified copper nanoparticle catalyst and electrode

Abstract

The invention relates to the technical field of copper nano particle electrocatalysts, in particular to a polyester modified copper nano particle catalyst and an electrode, the catalyst comprises copper nano particles and polyester adsorbed on the surfaces of the copper nano particles, the polyester accounts for 1-50% of the mass of the monolithic catalyst, and the polyester accounts for 1-50% of the mass of the monolithic catalyst. A catalytic system with a hydrophobic interface microenvironment and a reactant efficient confinement mass transfer channel is constructed with the conductive carrier, the catalyst for preparing the C2 + product through high-selectivity electro-catalysis CO2 reduction under high current density is achieved, and the problem that a traditional copper-based catalyst is low in C2 + product selectivity is solved; the construction strategy of the electrode is suitable for efficient CO2 resource utilization under the carbon neutralization background.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of copper nanoparticle electrocatalyst, in particular to a polyester modified copper nanoparticle catalyst and electrode. BACKGROUND

[0002] The massive combustion of fossil fuels has caused the concentration of carbon dioxide in the atmosphere to rise continuously, leading to climate warming, ocean acidification and other climate and environmental problems, which have attracted widespread attention. Electro-catalytic reduction of carbon dioxide can utilize green renewable power energy generated by solar energy, wind energy, water energy, etc., to realize the conversion of carbon dioxide emitted in industrial production and daily life into high-value-added C 2+ products such as ethylene, ethanol, acetic acid and propanol at normal temperature and pressure, realizing the storage of renewable power energy into chemical energy, and providing a promising strategy for closing the artificial carbon cycle and storing renewable energy. Copper-based catalysts are metal materials that can effectively catalyze the carbon-carbon (C-C) coupling to generate C 2+ products in the electro-catalytic reduction of carbon dioxide. For example, CN120099542A discloses a method for electro-catalytic reduction of carbon dioxide and membrane coupling production of ethanol, which uses a copper-based catalyst, a silver-based catalyst, a tin-based catalyst, a nickel-based catalyst, or a zinc-based catalyst. However, even if a ethanol-permeable membrane is arranged in the electrolytic cell, the faradic efficiency of ethanol is only increased to 44.53%, so it is still a challenge to regulate the high selectivity of C 2+ products.

[0003] To improve the product selectivity of copper-based catalysts, researchers have tried to change the crystal face structure of the catalyst, introduce alloys, and dope non-metallic elements to achieve the improvement of C 2+ product selectivity from the perspective of electronic structure thermodynamics. However, the common point of these strategies is to achieve the selective generation of C 2+ products by improving the adsorption bonding strength of reactants and reaction intermediates on the surface of the catalyst. For example, CN115821318B discloses a copper-based catalyst, a copper-based catalytic electrode, a preparation method thereof, and an electrochemical electrolysis device. In addition to copper elements, it also contains a regulator metal element with a larger atomic radius than copper. The faradic efficiency of the final product, n-propanol, is only 46% at most. This type of catalyst ignores the fact that the electro-catalytic reduction of carbon dioxide is a complex gas-liquid-solid three-phase interface reaction. The efficient mass transfer of carbon dioxide reactants as the starting step of the reaction will affect the reaction process and thus the selectivity of the products.

[0004] Currently, many documents report the use of hydrophobic silane coupling agents, thiol molecules and other molecules to graft and modify the surface of the catalyst to construct a hydrophobic interface microenvironment to promote the mass transfer of carbon dioxide molecules, improve the CO2 / H2O distribution ratio at the electrode-electrolyte interface, and realize the selective generation of C 2+Product selectivity. As CN116196932A discloses a carbon dioxide hydrogenation catalyst and its preparation method and application, the preparation method comprises the following steps: co-precipitation of copper source, zinc source and aluminum source with alkaline precipitant to obtain precipitate; the precipitate is sequentially filtered, washed, dried and calcined to obtain a precursor; the precursor is dispersed in a modifier solution to form a slurry, heated to reflux to obtain a catalyst; wherein the modifier solution contains a modifier selected from at least one of stearic acid, methyltrichlorosilane and silane coupling agent. However, the above grafting modification strategy of organic molecules can change the surface electronic structure of the metal catalyst, block the catalytic reaction site and cause low catalytic activity of the catalyst. At the same time, there are also studies on coating cationic polymers on the surface of copper nanoparticles to obtain catalysts, such as CN120041883A discloses a cationic polymer-coated copper-based catalyst and its preparation method and application, adding copper nanoparticles to the quaternary ammonium spiral piperazine solution, stirring uniformly and adjusting the pH to 9-13, then adding 1,3,5-benzene trichloroformic acid solution to react to obtain a cationic polymer-coated copper-based catalyst. However, it can only achieve a faradic efficiency of only 50% at a current density of 250mA / cm 2 Therefore, it is still a challenge to construct a catalytic system with a hydrophobic interface microenvironment and a high-efficiency limited mass transfer channel for reactants.

[0005] Based on the above, there are technical problems in the prior art that the copper-based catalyst has low faradic efficiency and low selectivity when catalyzing the conversion of carbon dioxide into C 2+ products. SUMMARY

[0006] To solve the above technical problems, the present application provides a polyester-modified copper nanoparticle catalyst, which comprises copper nanoparticles and a polyester adsorbed on the surface of the copper nanoparticles, and the mass percentage of the polyester in the whole catalyst is 1-50%.

[0007] Further, the polyester comprises an alkyl chain connected to an ester group (-COO-), and the number of carbon atoms in the alkyl chain is n, wherein n is an integer from 1 to 24.

[0008] Further, n is preferably an integer from 1 to 22.

[0009] Further, the polyester is a polyacrylate polymer and / or a polymethacrylate polymer.

[0010] Further, the polyacrylate polymer includes, but is not limited to, one or more of poly(methyl acrylate), poly(ethyl acrylate), poly(n-propyl acrylate), poly(i-propyl acrylate), poly(n-butyl acrylate), poly(i-butyl acrylate), poly(n-pentyl acrylate), poly(i-pentyl acrylate), poly(hexyl acrylate), poly(n-octyl acrylate), poly(i-octyl acrylate), poly(n-decyl acrylate), poly(dodecyl acrylate), poly(myristyl acrylate), poly(hexadecyl acrylate), poly(octadecyl acrylate), and poly(docosyl acrylate).

[0011] Further, the polymethacrylate polymer includes, but is not limited to, one or more of poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(i-propyl methacrylate), poly(n-butyl methacrylate), poly(i-butyl methacrylate), poly(hexyl methacrylate), poly(n-octyl methacrylate), poly(i-octyl methacrylate), poly(n-decyl methacrylate), poly(dodecyl methacrylate), poly(myristyl methacrylate), poly(hexadecyl methacrylate), poly(octadecyl methacrylate), and poly(docosyl methacrylate).

[0012] Further, the copper nanoparticles have a particle size of 100-300 nm.

[0013] The present application provides a preparation method of the polyester-modified copper nanoparticle catalyst, which includes preparing copper nanoparticles by a chemical reduction method, preparing a polyester by a thermal-initiated radical polymerization, and coating the polyester on the surface of the copper nanoparticles.

[0014] Further, the preparation method specifically includes the following steps: Step 1, preparing copper nanoparticles: dissolving copper sulfate and polyvinylpyrrolidone in deionized water, uniformly dispersing, and then sequentially adding ammonia solution, sodium hydroxide solution, and hydrazine hydrate solution under constant temperature conditions, to obtain the copper nanoparticles after the reaction is completed; Step 2, preparing a polyester: dissolving a polyester monomer in an organic solvent to obtain a monomer solution, and then adding a thermal initiator, to obtain the polyester after polymerization is completed; Step 3, preparing catalyst slurry: adding the copper nanoparticles and the polyester into a configuration solvent to disperse into a uniform catalyst slurry; Step 4, drying the catalyst slurry to obtain the catalyst.

[0015] Further, in Step 1, the mass ratio of the copper sulfate to the polyvinylpyrrolidone is (0.5-1):(1.5-2).

[0016] Further, in Step 1, the mass-to-volume ratio of the copper sulfate to the deionized water is (0.5-1):100 g / mL.

[0017] Further, the dispersion in step 1 is ultrasonic dispersion, the power of the ultrasonic dispersion is 250-300 W, and the time is 10-15 min.

[0018] Further, the temperature of the constant temperature in step 1 is 30-40℃.

[0019] Further, the way of adding the sodium hydroxide solution and the hydrazine hydrate solution in step 1 is dropwise adding.

[0020] Further, the stirring is needed between the adding of the ammonia solution, the sodium hydroxide solution and the hydrazine hydrate solution in step 1, and the stirring time is independently 10-30 min.

[0021] Further, the concentration of the ammonia solution in step 1 is 0.1-0.2 M.

[0022] Further, the volume ratio of the deionized water and the ammonia solution in step 1 is 10: (2-4).

[0023] Further, the concentration of the sodium hydroxide solution in step 1 is 1-1.5 M.

[0024] Further, the concentration of the hydrazine hydrate solution in step 1 is 10-15 M.

[0025] Further, the volume ratio of the ammonia solution, the sodium hydroxide solution and the hydrazine hydrate solution in step 1 is (15-20):(3-4):(1-2).

[0026] Further, the time of the reaction in step 1 is 2-3 h.

[0027] Further, after the reaction in step 1 is completed, the post-treatment is further included, and the post-treatment includes centrifugation, washing and drying.

[0028] Further, the centrifugation is at a speed of 8000-10000 r / min for 5-8 min.

[0029] Further, the solvent used in the washing is an organic solvent.

[0030] Further, the organic solvent includes but is not limited to ethanol.

[0031] Further, the drying is performed under vacuum, the vacuum degree is -100 to -90 kPa, the temperature is 60-80℃, and the time is 12-20 h.

[0032] Further, the polyester monomer in step 2 is an acrylate monomer and / or a methacrylate monomer.

[0033] Further, the acrylate monomer includes, but is not limited to, one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and docosyl acrylate.

[0034] Further, the methacrylate monomer includes, but is not limited to, one or more of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, and docosyl methacrylate.

[0035] Further, the solvent in step 2 is toluene or an alkane solvent.

[0036] Further, the mass content of the monomer in the monomer solution in step 2 is 30-60%.

[0037] Further, the thermal initiator in step 2 is dibenzoyl peroxide.

[0038] Further, the mass of the thermal initiator in step 2 is 0.5-1% of the mass of the monomer.

[0039] Further, the temperature of the polymerization in step 2 is 80-90°C, and the time is 2-3h.

[0040] Further, step 2 further includes purification of the polymerization product after the polymerization is completed.

[0041] Further, the purification includes washing and drying.

[0042] Further, the washing uses a washing agent of methanol or ethanol.

[0043] Further, the drying is at a temperature of 60-70°C for 2-2.5h.

[0044] Further, step 3 includes dissolving the polyester to prepare a polyester solution before adding the polyester to the configuration solvent.

[0045] Further, the mass concentration of the polyester in the polyester solution is 0.5-2%.

[0046] Further, the solvent in the polyester solution is isopropyl alcohol or n-hexane.

[0047] Further, the configuration solvent in step 3 is isopropyl alcohol or n-hexane.

[0048] Further, the volume ratio of the configuration solvent and the polyester solution in step 3 is (90-100):(8-9).

[0049] Further, the mass-volume ratio of the copper nanoparticles and the configuration solvent in step 3 is (10-15):(900-950) mg / μL.

[0050] Further, the dispersion in step 3 is ultrasonic dispersion, the power of the ultrasonic dispersion is 250-300 W, and the time is 30-40 min.

[0051] Further, the drying in step 4 is performed under vacuum conditions, the vacuum degree is-100 to-90 kPa, the drying temperature is 55-65℃, and the time is 2-3 h.

[0052] The application further provides a polyester-modified copper nanoparticle catalyst slurry, wherein the polyester-modified copper nanoparticles are the catalyst slurry in the polyester-modified copper nanoparticle catalyst.

[0053] Further, the catalyst slurry further comprises a slurry solvent.

[0054] Further, the slurry solvent includes but is not limited to alkanes.

[0055] Further, the slurry solvent is acetone or isopropyl alcohol or n-hexane.

[0056] The application further provides an electrode comprising a polyester-modified copper nanoparticle catalyst loaded on the surface of a conductive substrate or prepared from the polyester-modified copper nanoparticle catalyst slurry.

[0057] The application further provides a preparation method of an electrode, comprising: dropping and coating the polyester-modified copper nanoparticle catalyst slurry on a conductive carrier, and volatilizing the solvent in the catalyst slurry after drying, so that the catalyst is loaded on the surface of the conductive substrate to obtain the electrode.

[0058] Further, the conductive carrier includes but is not limited to a carbon paper-based gas diffusion layer.

[0059] Further, the dropping and coating process comprises twice dropping and coating the polyester-modified copper nanoparticle catalyst slurry on the conductive carrier, while ensuring that the temperature of the conductive carrier is maintained at 80-85℃, wherein the loading amount of the catalyst slurry on the conductive carrier is 1-1.5 mg / cm 2 .

[0060] Further, after the drop coating is completed, drying is performed under vacuum conditions, the vacuum degree is -100 to -90 kPa, the drying temperature is 55-65℃, and the drying time is 1.5-2h.

[0061] The application also provides a C 2+ product. 2+ The C 2+ product is prepared by electrocatalytic reduction of carbon dioxide using the electrode.

[0062] The application also provides a preparation method of the C 2+ product.

[0063] Further, the C 2+ product includes but is not limited to one or more of ethylene, ethanol, acetic acid, and propanol.

[0064] Further, the C 2+ product has a Faraday efficiency of 45-90% at a current density of 200-1000 mA / cm 2 .

[0065] Further, the electrolyte used in the electrolysis process is 1M KOH aqueous solution.

[0066] Further, the C 2+ product is prepared with by-product hydrogen, and the hydrogen has a Faraday efficiency of 2-40% at a current density of 200-1000 mA / cm 2 .

[0067] The application has the following beneficial effects: 1. The application provides a polyester-modified copper nanoparticle catalyst, which includes copper nanoparticles and polyester adsorbed on the surface of the copper nanoparticles, and the mass percentage of the polyester in the whole catalyst is 1-50%. The catalyst and a conductive carrier construct a catalytic system with a hydrophobic interface microenvironment and a high-efficiency limited mass transfer channel of reactants, and realize high-selectivity electrocatalytic reduction of CO2 to prepare C 2+ products at a high current density, effectively improve the selectivity of C 2+ products, and have the following advantages. 2. The technical scheme of the application includes constructing a polyester-modified copper nanoparticle composite electrode with different hydrophobicities, and constructing a high-efficiency side-chain ordered limited transport channel to realize the superfluid-like rapid diffusion mass transfer behavior of reactants, thereby significantly improving the selectivity of C 2+The product Faraday efficiency and reaction current density; the constructed confined mass transfer channels between hydrophobic ordered side chains, while ensuring a stable and efficient gas-liquid-solid three-phase interface, also possess the unique advantage of promoting the rapid diffusion of CO2 to the catalyst reaction site in a near-superfluid transport state at the three-phase interface, significantly improving catalyst activity and the production of high-value-added multi-carbon products such as ethylene and ethanol (C 2+ The selectivity of the product was improved, and the catalytic system achieved 800 mA / cm² in a gas diffusion-flow cell reactor. 2 At current density, C 2+ The product has a Faraday efficiency of up to 89.19%, and this electrode construction strategy is suitable for efficient CO2 resource utilization under carbon neutrality. Attached Figure Description

[0068] Figure 1 Scanning electron microscope (SEM) image of the copper nanoparticles prepared in this invention; Figure 2 The electrode electrocatalytic carbon dioxide reduction reaction C in Examples 4, 24, 28, and 32 of this invention. 2+ Comparison chart of product selectivity performance test results; Figure 3 This is a comparison chart showing the test results of the selectivity performance of hydrogen (H2), a byproduct of the electrode electrocatalytic carbon dioxide reduction reaction, in Examples 4, 24, 28, and 32 of the present invention. Figure 4 This is a graph showing the test results of the selectivity performance of the electrode electrocatalytic carbon dioxide reduction reaction products in Example 12 of the present invention; Figure 5 These are X-ray diffraction characterization diagrams of the electrodes in embodiments 3, 23, 27, and 31 of the present invention. Detailed Implementation

[0069] Example 1 This embodiment provides a polyester-modified copper nanoparticle catalyst and its preparation method. The catalyst consists of copper nanoparticles and hexadecyl acrylate adsorbed on the surface of the copper nanoparticles, wherein the hexadecyl acrylate accounts for 5% of the total mass of the catalyst. Figure 1 As shown, the copper nanoparticles have a particle size of 100-300 nm. The preparation method of the above-mentioned polyester-modified copper nanoparticle catalyst specifically includes the following steps: Step 1, preparation of copper nanoparticles: 0.998 g CuSO4·5H2O, 1.6 g polyvinylpyrrolidone was dissolved in 100 mL of deionized water, ultrasonic dispersion into a uniform solution, the power of the ultrasonic dispersion was 250 W, the time was 10 min, 30 mL of 0.15 M ammonia water solution was added under the condition of constant temperature water bath 35℃, after stirring for 15 min, 6 mL of 1.2 M NaOH solution was added dropwise and stirred for 20 min, finally 2 mL of 10 M N2H4·H2O solution was added dropwise, the reaction was completed after 2 h, centrifuged at a speed of 10000 r / min for 5 min, then washed with anhydrous ethanol for three times, finally dried under the condition of vacuum degree-100 kPa and temperature 60℃ for 12 h to obtain the copper nanoparticles; Step 2, preparation of polyester: first, 2.3131 g of hexadecyl acrylate monomer was weighed, and a monomer solution with a mass content of 50% was prepared with n-hexane as the alkane solvent, then 0.5% of the mass of the monomer was added to the solution as a thermal initiator, and the solution was polymerized in an oven at 80℃ for 2 hours to obtain a polymerization product. The polymerization product was washed with ethanol for 3-5 times to remove unreacted monomers and impurities, and then dried at a temperature of 60℃ for 2 h to obtain hexadecyl acrylate. Step 3, preparation of catalyst slurry: first, the hexadecyl acrylate was dissolved in n-hexane to prepare a 1% mass concentration hexadecyl acrylate solution; 10 mg of the copper nanoparticles and 83 μL of the hexadecyl acrylate solution were added to 917 μL of n-hexane as the solvent, and then ultrasonic dispersion was carried out under the condition of power 250 W for 30 min to obtain a uniform catalyst slurry; Step 4, preparation of catalyst: vacuum drying was carried out under the condition of vacuum degree-100 kPa and drying temperature 50℃ for 2 h to obtain the hexadecyl acrylate modified copper nanoparticle catalyst.

[0070] Example 2 The present embodiment provides a hexadecyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in step 3 of example 1. In the catalyst slurry, the slurry solvent is n-hexane.

[0071] Example 3 The present embodiment provides an electrode prepared from the hexadecyl acrylate modified copper nanoparticle catalyst slurry in example 2, which comprises: the hexadecyl acrylate modified copper nanoparticle catalyst slurry is drop-coated on a conductive carrier carbon paper-based gas diffusion layer using a pipette gun at an amount of 50 μL each time, while ensuring that the temperature of the conductive carrier is maintained at 80℃. In the present embodiment, the loading amount of the catalyst slurry on the conductive carrier is 1 mg / cm 2, the conductive carrier is purchased from SGL Carbon in Germany, the model number is SGL-28BC, after drop coating is completed, drying is performed in a vacuum condition, the vacuum degree is -100 kPa, the temperature is 50℃, and the time is 2h, after drying, the n-hexane in the catalyst slurry volatilizes, the polyhexadecyl acrylate modified copper nanoparticle catalyst (Cu@PHA) is loaded on the surface of the conductive substrate, and the electrode is obtained.

[0072] Example 4 In this embodiment, the electrode in Example 3 is used as a working electrode, and an aqueous KOH solution of 1M is used as an electrolyte, and an electrocatalytic CO2 reduction reaction is performed in an existing flow electrolysis cell to obtain C 2+ The catalyst loaded on the electrode has hydrophobicity, that is, the polyacrylate is a hydrophobic polymer chain, which can effectively construct a hydrophobic microenvironment of the catalyst-electrolyte interface, and regulate the CO2 / H2O distribution ratio at the interface. The confined mass transfer channel between the hydrophobic ordered side chains constructed by PHA has a unique advantage of promoting the rapid diffusion of CO2 at the gas-liquid-solid three-phase interface to the catalyst reaction site in a superfluid-like transmission state, significantly improving the catalyst activity and the selectivity of high-value-added multi-carbon products (C 2+ , and the highest C 2 product faraday efficiency reaches 89.19%, so it can be seen that the electrode prepared by the application is suitable for efficient CO2 resource utilization under the background of carbon neutralization. 2+

[0073] Example 5 The catalyst is composed of copper nanoparticles and polyhexadecyl acrylate adsorbed on the surface of the copper nanoparticles, and the mass percentage of the polyhexadecyl acrylate in the whole catalyst is 1%. The particle size of the copper nanoparticles is 100-300 nm. Compared with Example 1, the volume of the polyhexadecyl acrylate solution and n-hexane in the preparation of the catalyst slurry in step 3 in Example 1 is replaced by 16 μL and 984 μL respectively, and the remaining raw materials, reagents, dosage and conditions in the remaining preparation method are the same as those in Example 1. Finally, 1% polyhexadecyl acrylate modified copper nanoparticle catalyst in this embodiment is obtained.

[0074] Example 6 This embodiment provides a 1wt% polyhexadecyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Example 5. The slurry solvent in the catalyst slurry is n-hexane.

[0075] Example 7​ This embodiment provides an electrode prepared from the 1wt% polyhexyl acrylate modified copper nanoparticle catalyst slurry of Example 6. The other raw materials, reagents, amounts and conditions used are the same as in Example 3, and the electrode is obtained.

[0076] Example 8 Using the electrode from Example 7 as the working electrode, the test current density range was 200-800 mA / cm². 2 C 2+ The product is produced at a current density of 200-800 mA / cm². 2 The Faraday efficiency is 50-85% at 500 mA / cm². 2 At current density, C 2+ The product achieved a maximum Faraday efficiency of 80.79%. The electrolyte type, concentration, and apparatus used were consistent with those described in Example 4.

[0077] Example 9 This embodiment provides a polyester-modified copper nanoparticle catalyst and its preparation method. The catalyst consists of copper nanoparticles and polyhexyl acrylate adsorbed on the surface of the copper nanoparticles. The polyhexyl acrylate accounts for 3% of the total catalyst mass, and the copper nanoparticles have a particle size of 100-300 nm. Compared with Example 1, in this embodiment, the volumes of polyhexyl acrylate solution and n-hexane used to prepare the catalyst slurry in step 3 of Example 1 are replaced with 49 μL and 951 μL, respectively. The remaining raw materials, reagents, amounts, and conditions in the other preparation methods are the same as in Example 1, and the 3% polyhexyl acrylate-modified copper nanoparticle catalyst of this embodiment is finally obtained.

[0078] Example 10 This embodiment provides a 3wt% polyhexadecimall-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Example 9. The solvent in the catalyst slurry is n-hexane.

[0079] Example 11 This embodiment provides an electrode prepared from the 3wt% polyhexyl acrylate modified copper nanoparticle catalyst slurry of Example 10. The other raw materials, reagents, amounts and conditions used are the same as in Example 3, and the electrode is obtained.

[0080] Example 12 This embodiment uses the electrode from Embodiment 11 as the working electrode, such as... Figure 4 As shown, the test current density range is 200-1000 mA / cm². 2 C 2+The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2+ The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2+ The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm

[0081] Example 13 The present embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyhexadecyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyhexadecyl acrylate in the whole catalyst is 7%, and the particle size of the copper nanoparticles is 100-300 nm. Compared with Example 1, the volume of the polyhexadecyl acrylate solution and n-hexane in the preparation of the catalyst slurry in step 3 in Example 1 is replaced by 119 μL and 881 μL respectively, and the remaining raw materials, reagents, amount, and conditions in the preparation method are the same as those in Example 1. Finally, a 7% polyhexadecyl acrylate-modified copper nanoparticle catalyst in the present embodiment is obtained.

[0082] Example 14 The present embodiment provides a 7wt% polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Example 13. The slurry solvent in the catalyst slurry is n-hexane.

[0083] Example 15 The present embodiment provides an electrode prepared from the 7wt% polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in Example 14, and the remaining raw materials, reagents, amount, and conditions are the same as those in Example 3. The electrode is obtained.

[0084] Example 16 The electrode in Example 15 is used as a working electrode to test the current density in the range of 200-800 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2+ The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2 The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm 2+ The product has a Faraday efficiency of 40-90% at a current density of 200-1000 mA / cm

[0085] Example 17 The present example provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof, the catalyst is composed of copper nanoparticles and polyhexadecyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyhexadecyl acrylate in the whole catalyst is 10%, and the particle size of the copper nanoparticles is 100-300 nm. Compared with Example 1, the volume of the polyhexadecyl acrylate solution and n-hexane in the preparation of the catalyst slurry in step 3 in Example 1 is replaced by 175 μL and 825 μL respectively, and the remaining raw materials, reagents, amount and conditions in the preparation method are the same as those in Example 1. Finally, a 10% polyhexadecyl acrylate-modified copper nanoparticle catalyst in the present example is obtained.

[0086] Example 18 The present example provides a 10wt% polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Example 17. Among them, the slurry solvent in the catalyst slurry is n-hexane.

[0087] Example 19 The present example provides an electrode prepared from the 10wt% polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in Example 18, and the remaining raw materials, reagents, amount and conditions are the same as those in Example 3. The electrode is obtained.

[0088] Example 20 The electrode in Example 19 is used as the working electrode, and the current density range is 200-1000 mA / cm 2 , C 2+ The product has a faradic efficiency of 50-85% between the current density of 200-1000 mA / cm 2 . The product has a faradic efficiency of 50-85% between the current density of 200-1000 mA / cm 2 . The product has a faradic efficiency of 50-85% between the current density of 200-1000 mA / cm 2+ . The product has a faradic efficiency of 50-85% between the current density of 200-1000 mA / cm

[0089] Example 21 This embodiment provides a polyester-modified copper nanoparticle catalyst and its preparation method. The catalyst consists of copper nanoparticles and poly(dodecyl acrylate) adsorbed on the surface of the copper nanoparticles. The poly(dodecyl acrylate) accounts for 5% of the total catalyst by mass, and the copper nanoparticles have a particle size of 100-300 nm. Compared with Example 1, this embodiment replaces the monomer in Example 1 with 1.8754 g of dodecyl acrylate. The remaining raw materials, reagents, amounts, and conditions in the preparation method are the same as in Example 1, and the poly(dodecyl acrylate)-modified copper nanoparticle catalyst (Cu@PLA) of this embodiment is finally obtained.

[0090] Example 22 This embodiment provides a poly(12-ethylhexyl) modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Example 21, wherein the slurry solvent in the catalyst slurry is n-hexane.

[0091] Example 23 This embodiment provides an electrode in which the polyhexyl acrylate modified copper nanoparticle catalyst slurry of Example 3 is replaced with the polydodecyl acrylate modified copper nanoparticle catalyst slurry of Example 22, while the other raw materials, proportions and preparation conditions remain unchanged.

[0092] Example 24 This embodiment uses the electrode from Example 7 as the working electrode, and the test current density range is 200-500 mA / cm². 2 C 2+ The product is produced at a current density of 200-500 mA / cm². 2 The Faraday efficiency is 70-85% between these values. At 300 mA / cm²... 2 At current density, C 2+ The product achieved a maximum Faraday efficiency of 81.59%. The electrolyte type, concentration, and apparatus used were consistent with those described in Example 4.

[0093] Example 25 This embodiment provides a polyester-modified copper nanoparticle catalyst and its preparation method. The catalyst consists of copper nanoparticles and polytetradecyl acrylate adsorbed on the surface of the copper nanoparticles. The polytetradecyl acrylate accounts for 5% of the total catalyst by mass, and the copper nanoparticles have a particle size of 100-300 nm. Compared with Example 1, this embodiment replaces the monomer in Example 1 with 2.0943 g of tetradecyl acrylate. The remaining raw materials, reagents, amounts, and conditions in the preparation method are the same as in Example 1, and the polytetradecyl acrylate-modified copper nanoparticle catalyst (Cu@PTA) of this embodiment is finally obtained.

[0094] Example 26 The present embodiment provides a polytetradecyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Embodiment 25, wherein the slurry solvent in the catalyst slurry is n-hexane.

[0095] Embodiment 27 The present embodiment provides an electrode, which is the electrode prepared in Embodiment 3, wherein the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in Embodiment 3 is replaced by the polytetradecyl acrylate modified copper nanoparticle catalyst slurry in Embodiment 26, and the other raw materials, proportions, and preparation conditions remain unchanged.

[0096] Embodiment 28 The electrode in Embodiment 27 is used as the working electrode, and the current density range is 200-500 mA / cm 2 , C 2+ The product has a Faraday efficiency of 70-90% at a current density of 200-500 mA / cm 2 . The product has a Faraday efficiency of up to 86.13% at a current density of 400 mA / cm 2 , C 2+ The electrolyte type, concentration, and device used are consistent with those described in Embodiment 4.

[0097] Embodiment 29 The present embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof, which is composed of copper nanoparticles and polyoctadecyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyoctadecyl acrylate in the overall catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. Compared with Embodiment 1, the monomer in Embodiment 1 is replaced by 2.5321 g of octadecyl acrylate, and the other raw materials, reagents, amounts, and conditions in the preparation method are the same as those in Embodiment 1, and finally the polyoctadecyl acrylate modified copper nanoparticle catalyst (Cu@PSA) in the present embodiment is obtained.

[0098] Embodiment 30 The present embodiment provides a polyoctadecyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in Embodiment 29, wherein the slurry solvent in the catalyst slurry is n-hexane.

[0099] Embodiment 31 The present embodiment provides an electrode, which is the electrode prepared in Embodiment 3, wherein the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in Embodiment 3 is replaced by the polyoctadecyl acrylate modified copper nanoparticle catalyst slurry, and the other raw materials, proportions, and preparation conditions remain unchanged.

[0100] Embodiment 32 This example is to use the electrode in example 31 as the working electrode, and the current density range is 200-1000 mA / cm 2 , C 2+ The product has a faradic efficiency of 45-80% at a current density of 200-1000 mA / cm 2 . At a current density of 1000 mA / cm 2 , C 2+ The product has a faradic efficiency of up to 77.27%. The electrolyte type, concentration, and device used are consistent with those described in example 4.

[0101] Example 33 This example provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly(methyl acrylate) adsorbed on the surface of the copper nanoparticles, and the mass percentage of the poly(methyl acrylate) in the overall catalyst is 5%. The particle size of the copper nanoparticles is 100-300 nm. In this example, the monomer in example 1 is replaced by 0.6717 g of methyl acrylate, toluene is used as the solvent, and methanol is used as the washing reagent to prepare the poly(methyl acrylate). The remaining raw materials, reagents, amounts, and conditions in the preparation method are the same as in example 1. Finally, the poly(methyl acrylate)-modified copper nanoparticle catalyst in this example is obtained.

[0102] The poly(methyl acrylate) is dissolved in acetone to prepare a poly(methyl acrylate) solution with a mass concentration of 1%. 10 mg of the copper nanoparticles and 70 μL of the poly(methyl acrylate) solution are added to 930 μL of acetone as the solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min at a power of 250 W. Vacuum drying is performed at a vacuum degree of -100 kPa and a drying temperature of 50°C for 2 h to obtain the poly(methyl acrylate)-modified copper nanoparticle catalyst.

[0103] Example 34 This example provides a poly(methyl acrylate)-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in example 33. In this example, the slurry solvent in the catalyst slurry is acetone.

[0104] Example 35 This example provides an electrode, in which the poly(hexadecyl acrylate)-modified copper nanoparticle catalyst slurry in example 3 is replaced by the poly(methyl acrylate)-modified copper nanoparticle catalyst slurry in example 34, and the remaining raw materials, proportions, and preparation conditions remain unchanged to obtain the electrode.

[0105] Example 36 The embodiment uses the electrode in embodiment 35 as the working electrode, and the current density range is 100-300 mA / cm 2 The electrolyte type, concentration, and device used are consistent with those described in embodiment 4.

[0106] Embodiment 37 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyethyl acrylate adsorbed on the surface of the copper nanoparticles, and the mass percentage of the polyethyl acrylate in the whole catalyst is 5%. The particle size of the copper nanoparticles is 100-300 nm.

[0107] In the embodiment, the monomer in embodiment 1 is replaced by 0.7811 g of ethyl acrylate, toluene is used as the solvent, and methanol is used as the washing reagent to prepare polyethyl acrylate. The remaining raw materials, reagents, dosages, and conditions in the preparation method are the same as those in embodiment 1. Finally, the polyethyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0108] The polyethyl acrylate is dissolved in acetone to prepare a polyethyl acrylate solution with a mass concentration of 1%. 10 mg of the copper nanoparticles and 70 μL of the polyethyl acrylate solution are added to 930 μL of acetone as the solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min at a power of 250 W. Vacuum drying is performed at a vacuum degree of -100 kPa and a drying temperature of 50°C for 2 h to obtain the polyethyl acrylate-modified copper nanoparticle catalyst.

[0109] Embodiment 38 The embodiment provides a polyethyl acrylate-modified copper nanoparticle catalyst slurry. The catalyst slurry is the catalyst slurry prepared in embodiment 37. In the catalyst slurry, the slurry solvent is acetone.

[0110] Embodiment 39 The embodiment provides an electrode. The polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in embodiment 3 is replaced by the polyethyl acrylate-modified copper nanoparticle catalyst slurry in embodiment 38, and the remaining raw materials, proportions, and preparation conditions remain unchanged to obtain the electrode.

[0111] Embodiment 40 The embodiment uses the electrode in embodiment 39 as the working electrode, and the current density range is 100-300 mA / cm 2 The electrolyte type, concentration, and device used are consistent with those described in embodiment 4.

[0112] Embodiment 41 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-propyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-propyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 0.8905 g of n-propyl acrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-propyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the poly-n-propyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0113] The poly-n-propyl acrylate is dissolved in acetone to prepare a poly-n-propyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the poly-n-propyl acrylate solution are added into 930 μL of acetone as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-propyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0114] Embodiment 42 The embodiment provides a poly-n-propyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 41. In the catalyst slurry, the slurry solvent is acetone.

[0115] Embodiment 43 The embodiment provides an electrode, in which the poly-n-hexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the poly-n-propyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 42, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0116] Embodiment 44 In the embodiment, the electrode in the embodiment 43 is used as a working electrode, and the current density range is 100-300 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0117] Embodiment 45 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisopropyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisopropyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 0.8905 g of isopropyl acrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polyisopropyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polyisopropyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0118] The polyisopropyl acrylate is dissolved in isopropyl alcohol to prepare a polyisopropyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polyisopropyl acrylate solution are added into 930 μL of acetone as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polyisopropyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0119] Embodiment 46 The embodiment provides a polyisopropyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 45. In the catalyst slurry, the slurry solvent is acetone.

[0120] Embodiment 47 The embodiment provides an electrode, in which the polyisopropyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 46 is used to replace the polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0121] Embodiment 48 The embodiment uses the electrode in the embodiment 47 as a working electrode, and the current density range is 100-300 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0122] Embodiment 49 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-butyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-butyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the catalyst in the embodiment 1 is replaced by 1.0000 g of n-butyl acrylate, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-butyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the poly-n-butyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0123] The poly-n-butyl acrylate is dissolved in isopropyl alcohol to prepare a poly-n-butyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the poly-n-butyl acrylate solution are added into 930 μL of isopropyl alcohol as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-butyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0124] Embodiment 50 The embodiment provides a poly-n-butyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 49. In the catalyst slurry, the slurry solvent is isopropyl alcohol.

[0125] Embodiment 51 The embodiment provides an electrode, in which the poly-n-butyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 50 is used to replace the poly-hexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0126] Embodiment 52 In the embodiment, the electrode in the embodiment 51 is used as a working electrode, and the current density range is 100-350 mA / cm 2 , the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0127] Embodiment 53 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisobutyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisobutyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the embodiment 1 is replaced by 1.0000 g of isobutyl acrylate, toluene is used as a solvent, and methanol is used as a washing reagent to prepare polyisobutyl acrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation method are the same as those in the embodiment 1. Finally, a polyisobutyl acrylate-modified copper nanoparticle catalyst is obtained.

[0128] The polyisobutyl acrylate is dissolved in isopropyl alcohol to prepare a polyisobutyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polyisobutyl acrylate solution are added into 930 μL of isopropyl alcohol as a solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polyisobutyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0129] Embodiment 54 The embodiment provides a polyisobutyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 53. In the catalyst slurry, the slurry solvent is isopropyl alcohol.

[0130] Embodiment 55 The embodiment provides an electrode, in which the polyisohexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polyisobutyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 54, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0131] Embodiment 56 The embodiment uses the electrode in the embodiment 55 as a working electrode, and tests the current density range to be 100-350 mA / cm 2 , the electrolyte type, the concentration and the device used are the same as those in the embodiment 4.

[0132] Embodiment 57 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-amyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-amyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.1094 g of n-amyl acrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-amyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the poly-n-amyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0133] The poly-n-amyl acrylate is dissolved in n-hexane to prepare a poly-n-amyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the poly-n-amyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-amyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0134] Embodiment 58 The embodiment provides a poly-n-amyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 57. In the catalyst slurry, the slurry solvent is n-hexane.

[0135] Embodiment 59 The embodiment provides an electrode, in which the poly-n-hexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the poly-n-amyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 58, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0136] Embodiment 60 The embodiment uses the electrode in the embodiment 59 as a working electrode, and tests the current density range of 100-350 mA / cm 2 , the type and concentration of the electrolyte, and the device used are the same as those described in the embodiment 4.

[0137] Embodiment 61 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisopentyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisopentyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.1094 g of isopentyl acrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polyisopentyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1. Finally, the polyisopentyl acrylate modified copper nanoparticle catalyst is obtained.

[0138] The polyisopentyl acrylate is dissolved in n-hexane to prepare a polyisopentyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polyisopentyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then ultrasonic dispersion is carried out for 30 min under the condition that the power is 250 W, to obtain a uniform catalyst slurry; vacuum drying is carried out for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃, to obtain the polyisopentyl acrylate modified copper nanoparticle catalyst.

[0139] Embodiment 62 The embodiment provides a polyisopentyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 61. In the catalyst slurry, the slurry solvent is n-hexane.

[0140] Embodiment 63 The embodiment provides an electrode, in which the polyisopentyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 62 is used to replace the polyisopentyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, to obtain the electrode.

[0141] Embodiment 64 The embodiment uses the electrode in the embodiment 63 as a working electrode, and tests the current density range to be 100-350 mA / cm 2 , the electrolyte type, the concentration and the device used are the same as those described in the embodiment 4.

[0142] Embodiment 65 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyhexyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyhexyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.2188 g of hexyl acrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polyhexyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polyhexyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0143] The polyhexyl acrylate is dissolved in n-hexane to prepare a polyhexyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polyhexyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polyhexyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0144] Embodiment 66 The embodiment provides a polyhexyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 65. In the catalyst slurry, the slurry solvent is n-hexane.

[0145] Embodiment 67 The embodiment provides an electrode, in which the polyhexyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 66 is used to replace the polyhexyl palmitate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0146] Embodiment 68 In the embodiment, the electrode in the embodiment 67 is used as a working electrode, and the current density range is 100-400 mA / cm 2 , the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0147] Embodiment 69 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-octyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-octyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the embodiment 1 is replaced by 1.4377 g of n-octyl acrylate, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-octyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the poly-n-octyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0148] The poly-n-octyl acrylate is dissolved in n-hexane to prepare a poly-n-octyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the poly-n-octyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-octyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0149] Embodiment 70 The embodiment provides a poly-n-octyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 69. In the catalyst slurry, the slurry solvent is n-hexane.

[0150] Embodiment 71 The embodiment provides an electrode, in which the poly-n-octyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 70 is used to replace the poly-n-hexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, the remaining raw materials, proportions and preparation conditions are unchanged, and the electrode is obtained.

[0151] Embodiment 72 The embodiment uses the electrode in the embodiment 71 as a working electrode, and the current density range is 200-400 mA / cm 2 , the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0152] Embodiment 73 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisooctyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisooctyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.4377 g of isooctyl acrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polyisooctyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1. Finally, a polyisooctyl acrylate-modified copper nanoparticle catalyst is obtained.

[0153] The polyisooctyl acrylate is dissolved in n-hexane to prepare a polyisooctyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polyisooctyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then ultrasonic dispersion is carried out for 30 min under the condition that the power is 250 W, to obtain a uniform catalyst slurry; vacuum drying is carried out for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃, to obtain a polyisooctyl acrylate-modified copper nanoparticle catalyst.

[0154] Embodiment 74 The embodiment provides a polyisooctyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 73. In the catalyst slurry, the slurry solvent is n-hexane.

[0155] Embodiment 75 The embodiment provides an electrode, in which the polyisooctyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 74 is used to replace the polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, to obtain the electrode.

[0156] Embodiment 76 The embodiment uses the electrode in the embodiment 75 as a working electrode, and tests the current density in the range of 200-400 mA / cm 2 , and the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0157] Embodiment 77 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and decyl polyacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the decyl polyacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.6566 g of decyl acrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare decyl polyacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the decyl polyacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0158] The decyl polyacrylate is dissolved in n-hexane to prepare a decyl polyacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the decyl polyacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the decyl polyacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0159] Embodiment 78 The embodiment provides a decyl polyacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 77. In the catalyst slurry, the slurry solvent is n-hexane.

[0160] Embodiment 79 The embodiment provides an electrode, in which the polyhexadecyl polyacrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the decyl polyacrylate modified copper nanoparticle catalyst slurry in the embodiment 78, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0161] Embodiment 80 The embodiment uses the electrode in the embodiment 79 as a working electrode, and tests the current density range of 200-500 mA / cm 2 , the type and concentration of the electrolyte, and the device used are the same as those in the embodiment 4.

[0162] Embodiment 81 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polydocosyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polydocosyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 2.9699 g of docosyl acrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the polydocosyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1. Finally, the polydocosyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0163] The polydocosyl acrylate is dissolved in n-hexane to prepare a polydocosyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polydocosyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polydocosyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0164] Embodiment 82 The embodiment provides a polydocosyl acrylate-modified copper nanoparticle catalyst slurry. The catalyst slurry is the catalyst slurry prepared in the embodiment 81. In the catalyst slurry, the slurry solvent is n-hexane.

[0165] Embodiment 83 The embodiment provides an electrode. The polydocosyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 82 is used to replace the polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0166] Embodiment 84 The embodiment uses the electrode in the embodiment 83 as a working electrode, and the current density range is 200-1000 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0167] Embodiment 85 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the catalyst in the embodiment 1 is replaced by 0.7811 g of methyl methacrylate, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polymethyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polymethyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0168] The polymethyl methacrylate is dissolved in acetone to prepare a polymethyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polymethyl methacrylate solution are added into 930 μL of acetone as a solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0169] Embodiment 86 The embodiment provides a polymethyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 85. In the catalyst slurry, the slurry solvent is acetone.

[0170] Embodiment 87 The embodiment provides an electrode, in which the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polymethyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 86, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0171] Embodiment 88 The embodiment uses the electrode in the embodiment 87 as a working electrode, and the current density range is 100-300 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0172] Embodiment 89 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethyl ethyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl ethyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 0.8905 g of ethyl methacrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polymethyl ethyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polymethyl ethyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0173] The polymethyl ethyl methacrylate is dissolved in acetone to prepare a polymethyl ethyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polymethyl ethyl methacrylate solution are added into 930 μL of acetone as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl ethyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0174] Embodiment 90 The embodiment provides a polymethyl ethyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 89. In the catalyst slurry, the slurry solvent is acetone.

[0175] Embodiment 91 The embodiment provides an electrode, which uses the polymethyl ethyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 90 to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions are unchanged, so that the electrode is obtained.

[0176] Embodiment 92 The embodiment uses the electrode in the embodiment 91 as a working electrode, and tests the current density range to be 100-300 mA / cm 2 , the electrolyte type, the concentration and the device used are the same as those described in the embodiment 4.

[0177] Embodiment 93 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethyl n-propyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl n-propyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the embodiment 1 is replaced by 1.0000 g of polymethyl n-propyl acrylate, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polymethyl n-propyl acrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation methods are the same as those in the embodiment 1, and finally the polymethyl n-propyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0178] The polymethyl n-propyl acrylate is dissolved in acetone to prepare a polymethyl n-propyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polymethyl n-propyl acrylate solution are added into 930 μL of acetone as a solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl n-propyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0179] Embodiment 94 The embodiment provides a polymethyl n-propyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 93. In the catalyst slurry, the slurry solvent is acetone.

[0180] Embodiment 95 The embodiment provides an electrode, in which the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polymethyl n-propyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 94, and the remaining raw materials, proportions and preparation conditions remain unchanged.

[0181] Embodiment 96 The embodiment uses the electrode in the embodiment 95 as a working electrode, and tests the current density range to be 100-300 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0182] Embodiment 97 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethyl isopropyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl isopropyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the embodiment 1 is replaced by 1.0000 g of isopropyl methacrylate, toluene is used as a solvent, and methanol is used as a washing reagent to prepare polymethyl isopropyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polymethyl isopropyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0183] The polymethyl isopropyl acrylate is dissolved in acetone to prepare a polymethyl isopropyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polymethyl isopropyl acrylate solution are added into 930 μL of acetone as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl isopropyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0184] Embodiment 98 The embodiment provides a polymethyl isopropyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 97. In the catalyst slurry, the slurry solvent is acetone.

[0185] Embodiment 99 The embodiment provides an electrode, in which the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polymethyl isopropyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 98, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0186] Embodiment 100 The embodiment uses the electrode in the embodiment 99 as a working electrode, and tests the current density range of 100-300 mA / cm 2 , the type and concentration of the electrolyte, and the device used are the same as those in the embodiment 4.

[0187] Embodiment 101 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-butyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-butyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.1094 g of n-butyl methacrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-butyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the poly-n-butyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0188] The poly-n-butyl methacrylate is dissolved in isopropyl alcohol to prepare a poly-n-butyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the poly-n-butyl methacrylate solution are added into 930 μL of isopropyl alcohol as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-butyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0189] Embodiment 102 The embodiment provides a poly-n-butyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 101. In the catalyst slurry, the slurry solvent is isopropyl alcohol.

[0190] Embodiment 103 The embodiment provides an electrode, which uses the poly-n-butyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 102 to replace the poly-n-hexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0191] Embodiment 104 The embodiment uses the electrode in the embodiment 103 as a working electrode, and tests the current density range of 100-350 mA / cm 2 , the type and concentration of the electrolyte, and the device used are the same as those described in the embodiment 4.

[0192] Embodiment 105 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisobutyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisobutyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.1094 g of isobutyl methacrylate is used to replace the monomer in the embodiment 1, toluene is used as a solvent, and methanol is used as a washing reagent to prepare the polyisobutyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polyisobutyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0193] The polyisobutyl methacrylate is dissolved in isopropyl alcohol to prepare a polyisobutyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 70 μL of the polyisobutyl methacrylate solution are added into 930 μL of isopropyl alcohol as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polyisobutyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0194] Embodiment 106 The embodiment provides a polyisobutyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 105. In the catalyst slurry, the slurry solvent is isopropyl alcohol.

[0195] Embodiment 107 The embodiment provides an electrode, which uses the polyisobutyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 106 to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0196] Embodiment 108 The embodiment uses the electrode in the embodiment 107 as a working electrode, and tests the current density in the range of 100-350 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0197] Embodiment 109 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof, the catalyst is composed of copper nanoparticles and polymethyl pentyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl pentyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In comparison with example 1, the monomer in example 1 is replaced by 1.2188 g of polymethyl pentyl acrylate, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the polymethyl pentyl acrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation methods are the same as those in example 1, and finally the polymethyl pentyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0198] The polymethyl pentyl acrylate is dissolved in n-hexane to prepare a polymethyl pentyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polymethyl pentyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl pentyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0199] Example 110 The embodiment provides a polymethyl pentyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in example 109. In the catalyst slurry, the slurry solvent is n-hexane.

[0200] Example 111 The embodiment provides an electrode, which replaces the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in example 3 with the polymethyl pentyl acrylate modified copper nanoparticle catalyst slurry in example 110, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0201] Example 112 The embodiment uses the electrode in example 111 as a working electrode, and the current density range is 100-350 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in example 4.

[0202] Example 113 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof, the catalyst is composed of copper nanoparticles and polymethyl isopentyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl isopentyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.2188 g of isopentyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polymethyl isopentyl acrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation methods are the same as those in the embodiment 1, and finally the polymethyl isopentyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0203] The polymethyl isopentyl acrylate is dissolved in n-hexane to prepare a polymethyl isopentyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polymethyl isopentyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl isopentyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0204] Embodiment 114 The embodiment provides a polymethyl isopentyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 113. In the catalyst slurry, the slurry solvent is n-hexane.

[0205] Embodiment 115 The embodiment provides an electrode, which uses the polymethyl isopentyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 114 to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0206] Embodiment 116 The embodiment uses the electrode in the embodiment 115 as a working electrode, and tests the current density in the range of 100-350 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0207] Embodiment 117 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethylhexyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethylhexyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.3283 g of hexyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polymethylhexyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polymethylhexyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0208] The polymethylhexyl acrylate is dissolved in n-hexane to prepare a polymethylhexyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polymethylhexyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethylhexyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0209] Embodiment 118 The embodiment provides a polymethylhexyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 117. In the catalyst slurry, the slurry solvent is n-hexane.

[0210] Embodiment 119 The embodiment provides an electrode, which uses the polymethylhexyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 118 to replace the polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0211] Embodiment 120 The embodiment uses the electrode in the embodiment 119 as a working electrode, and tests the current density range to be 100-400 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0212] Embodiment 121 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and poly-n-octyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the poly-n-octyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, the monomer in the embodiment 1 is replaced by 1.5472 g of n-octyl methacrylate, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the poly-n-octyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation method are the same as those in the embodiment 1, and finally the poly-n-octyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0213] The poly-n-octyl methacrylate is dissolved in n-hexane to prepare a poly-n-octyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the poly-n-octyl methacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the poly-n-octyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0214] Embodiment 122 The embodiment provides a poly-n-octyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 121. In the catalyst slurry, the slurry solvent is n-hexane.

[0215] Embodiment 123 The embodiment provides an electrode, in which the poly-n-octadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the poly-n-octyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 122, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0216] Embodiment 124 In the embodiment, the electrode in the embodiment 123 is used as a working electrode, and the current density range is 100-400 mA / cm 2 , the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0217] Embodiment 125 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyisooctyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyisooctyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.5472g of isooctyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the polyisooctyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polyisooctyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0218] The polyisooctyl methacrylate is dissolved in n-hexane to prepare a polyisooctyl methacrylate solution with a mass concentration of 1%; 10mg of the copper nanoparticles and 85μL of the polyisooctyl methacrylate solution are added into 915μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30min under the condition that the power is 250W; and the polyisooctyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2h under the condition that the vacuum degree is-100kPa and the drying temperature is 50℃.

[0219] Embodiment 126 The embodiment provides a polyisooctyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 125. In the catalyst slurry, the slurry solvent is n-hexane.

[0220] Embodiment 127 The embodiment provides an electrode, which uses the polyisooctyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 126 to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions are unchanged, so that the electrode is obtained.

[0221] Embodiment 128 The embodiment uses the electrode in the embodiment 127 as a working electrode, and the current density range is 100-400mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0222] Embodiment 129 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and decyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the decyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.7660 g of decyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare decyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the decyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0223] The decyl methacrylate is dissolved in n-hexane to prepare a decyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the decyl methacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the decyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 DEG C.

[0224] Embodiment 13 The embodiment provides a decyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 129. In the catalyst slurry, the slurry solvent is n-hexane.

[0225] Embodiment 13 The embodiment provides an electrode, which uses the decyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 130 to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions are unchanged, so that the electrode is obtained.

[0226] Embodiment 13 The embodiment uses the electrode in the embodiment 131 as a working electrode, and the current density range is 200-500 mA / cm 2 , the electrolyte type, concentration and device used are the same as those in the embodiment 4.

[0227] Embodiment 13 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof, the catalyst is composed of copper nanoparticles and polydodecyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polydodecyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 1.9849 g of dodecyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polydodecyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the remaining preparation method are the same as those in the embodiment 1, and finally the polydodecyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0228] The polydodecyl methacrylate is dissolved in n-hexane to prepare a polydodecyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polydodecyl methacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polydodecyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0229] Embodiment 13 The embodiment provides a polydodecyl methacrylate modified copper nanoparticle catalyst slurry, and the catalyst slurry is the catalyst slurry prepared in the embodiment 133. In the catalyst slurry, the slurry solvent is n-hexane.

[0230] Embodiment 13 The embodiment provides an electrode, wherein the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polydodecyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 134, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0231] Embodiment 13 The embodiment uses the electrode in the embodiment 135 as a working electrode, and the current density range is 200-500 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0232] Embodiment 13 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethyl tetradecyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethyl tetradecyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 2.2038 g of polymethyl tetradecyl acrylate is prepared by replacing the monomer in the embodiment 1 with polymethyl tetradecyl acrylate, using n-hexane as a solvent and methanol as a washing reagent. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1. Finally, the polymethyl tetradecyl acrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0233] The polymethyl tetradecyl acrylate is dissolved in n-hexane to prepare a polymethyl tetradecyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polymethyl tetradecyl acrylate solution are added into 915 μL of n-hexane as a solvent, and a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethyl tetradecyl acrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0234] Embodiment 138 The embodiment provides a polymethyl tetradecyl acrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 137. In the catalyst slurry, the slurry solvent is n-hexane.

[0235] Embodiment 139 The embodiment provides an electrode, which replaces the polymethyl tetradecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 138 with the polymethyl tetradecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0236] Embodiment 140 The embodiment uses the electrode in the embodiment 139 as a working electrode, and the current density range is 200-500 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0237] Embodiment 141 The embodiment provides a polyester-modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polymethylhexadecyl acrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polymethylhexadecyl acrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 2.4227 g of hexadecyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polymethylhexadecyl acrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polymethylhexadecyl acrylate-modified copper nanoparticle catalyst in the embodiment is obtained.

[0238] The polymethylhexadecyl acrylate is dissolved in n-hexane to prepare a polymethylhexadecyl acrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polymethylhexadecyl acrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polymethylhexadecyl acrylate-modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0239] Embodiment 14 The embodiment provides a polymethylhexadecyl acrylate-modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 141. In the catalyst slurry, the slurry solvent is n-hexane.

[0240] Embodiment 143 The embodiment provides an electrode, which uses the polymethylhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 142 to replace the polyhexadecyl acrylate-modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions are unchanged, so that the electrode is obtained.

[0241] Embodiment 144 The embodiment uses the electrode in the embodiment 143 as a working electrode, and tests the current density in the range of 200-1000 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0242] Embodiment 145 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polyoctadecyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polyoctadecyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 2.6416 g of octadecyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare polyoctadecyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polyoctadecyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0243] The polyoctadecyl methacrylate is dissolved in n-hexane to prepare a polyoctadecyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polyoctadecyl methacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polyoctadecyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0244] Embodiment 14 The embodiment provides a polyoctadecyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 145. In the catalyst slurry, the slurry solvent is n-hexane.

[0245] Embodiment 14 The embodiment provides an electrode, in which the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3 is replaced by the polyoctadecyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 146, and the remaining raw materials, proportions and preparation conditions remain unchanged, so that the electrode is obtained.

[0246] Embodiment 14 The embodiment uses the electrode in the embodiment 147 as a working electrode, and the current density range is 200-1000 mA / cm 2 , the electrolyte type, concentration and device used are the same as those described in the embodiment 4.

[0247] Embodiment 14 The embodiment provides a polyester modified copper nanoparticle catalyst and a preparation method thereof. The catalyst is composed of copper nanoparticles and polydocosyl methacrylate adsorbed on the surface of the copper nanoparticles, the mass percentage of the polydocosyl methacrylate in the whole catalyst is 5%, and the particle size of the copper nanoparticles is 100-300 nm. In the embodiment, 3.0793 g of docosyl methacrylate is used to replace the monomer in the embodiment 1, n-hexane is used as a solvent, and methanol is used as a washing reagent to prepare the polydocosyl methacrylate. The remaining raw materials, reagents, dosages and conditions in the preparation method are the same as those in the embodiment 1, and finally the polydocosyl methacrylate modified copper nanoparticle catalyst in the embodiment is obtained.

[0248] The polydocosyl methacrylate is dissolved in n-hexane to prepare a polydocosyl methacrylate solution with a mass concentration of 1%; 10 mg of the copper nanoparticles and 85 μL of the polydocosyl methacrylate solution are added into 915 μL of n-hexane as a solvent, and then a uniform catalyst slurry is obtained after ultrasonic dispersion for 30 min under the condition that the power is 250 W; and the polydocosyl methacrylate modified copper nanoparticle catalyst is obtained by vacuum drying for 2 h under the condition that the vacuum degree is -100 kPa and the drying temperature is 50 ℃.

[0249] Embodiment 15 The embodiment provides a polydocosyl methacrylate modified copper nanoparticle catalyst slurry, which is the catalyst slurry prepared in the embodiment 149. In the catalyst slurry, the slurry solvent is n-hexane.

[0250] Embodiment 15 The embodiment provides an electrode, in which the polydocosyl methacrylate modified copper nanoparticle catalyst slurry in the embodiment 150 is used to replace the polyhexadecyl acrylate modified copper nanoparticle catalyst slurry in the embodiment 3, and the remaining raw materials, proportions and preparation conditions remain unchanged.

[0251] Embodiment 15 The embodiment uses the electrode in the embodiment 151 as a working electrode, and the current density range is 200-1000 mA / cm 2 , the type and concentration of the electrolyte and the used device are the same as those in the embodiment 4.

[0252] Test example 1 The electrodes prepared in the embodiments 3, 23, 27 and 31 are subjected to X-ray diffraction, and the results are as follows. Figure 5As shown, the four electrodes showed different X-ray diffraction signals. PLA and PTA with shorter side chains only detected the crystallization signal related to Cu nanoparticles, while PHA and PSA with longer side chains showed new polyacrylate diffraction peaks, indicating that the two polymers had crystalline morphology in the composite electrode and formed a unique ordered nano-limited structure of regular carbon side chains.

[0253] Test Example 2 The selectivity performance of the byproduct hydrogen in the electrocatalytic reduction of carbon dioxide of the electrodes of Examples 4, 24, 28 and 32 described above was tested, and the test results are shown in Table 3. 2+ The product selectivity performance was tested, and the test results are shown in Table 2. Figure 2 As shown, the four different electrodes exhibited different electrochemical activities and C 2+ product selectivity. Specifically, the composite electrode modified by PLA with shorter side chains was suitable for a current density range of 200-400 mA / cm 2 , and the maximum selectivity appeared at a current density of 350 mA / cm 2 , achieving a C 2+ product faradic efficiency of nearly 80%; the electrode modified by PTA with 14 side chain carbon atoms had an expanded current density range of 200-500 mA / cm 2 , and the maximum C 2+ product faradic efficiency appeared at a current density of 400 mA / cm 2 , being about 85%; when the carbon side chain length of the hydrophobic polymer was increased to 16 and 18, the electrode had a further expanded current density range of 200-1000 mA / cm 2 , in which the composite electrode modified by PHA achieved a C 2 product faradic efficiency of nearly 90% at a current density of 800 mA / cm 2+ , while the composite electrode modified by PSA with a higher carbon side chain length had a reduced faradic efficiency, and the highest C 2 product faradic efficiency was only nearly 75% at a current density of 800 mA / cm 2+ .

[0254] Test Example 3 The selectivity performance of the byproduct hydrogen in the electrocatalytic reduction of carbon dioxide of the electrodes of Examples 4, 24, 28 and 32 described above was tested, and the test results are shown in Table 3. Figure 3 As shown, the four different electrodes exhibited different selectivity to the byproduct H2. Specifically, the composite electrode modified by PLA with shorter side chains still had a relatively high H2 faradic efficiency at a low current density of 200-400 mA / cm 2 , while the faradic efficiency of H2 of PTA, PHA and PSA with longer side chains was reduced at a higher current density. In particular, the electrodes modified by PHA and PSA had a current density of 800 mA / cm2 The faradaic efficiency of H2remains at a low level at high current densities.

[0255] It is to be understood that the application is not limited to what has been described above and illustrated in the drawings. Modifications and changes can be made without departing from its scope. The scope of the application is limited only by the claims that follow.

Claims

1. A polyester-modified copper nanoparticle catalyst characterized in that, The catalyst comprises copper nanoparticles and polyester adsorbed on the surface of the copper nanoparticles, and the mass percentage of the polyester in the whole catalyst is 1-50%.

2. The polyester-modified copper nanoparticle catalyst of claim 1, wherein, The polyester comprises an alkyl chain connected with an ester group, and the number of carbon atoms in the alkyl chain is n, wherein n is an integer from 1 to 24.

3. The polyester-modified copper nanoparticle catalyst of claim 1, wherein, The particle size of the copper nanoparticles is 100-300 nm.

4. A method of preparing the polyester-modified copper nanoparticle catalyst of any one of claims 1-3, characterized in that, The preparation method comprises the following steps:

5. The method of claim 4, wherein the polyester-modified copper nanoparticle catalyst is prepared by the steps of: (a) providing a copper nanoparticle; (b) providing a polyester; (c) mixing the copper nanoparticle and the polyester to form a mixture; and (d) heating the mixture to form the polyester-modified copper nanoparticle catalyst. The preparation method comprises the following steps: Step 1, preparation of copper nanoparticles: copper sulfate and polyvinylpyrrolidone are dissolved in deionized water, and then ammonia solution, sodium hydroxide solution and hydrazine hydrate solution are added in sequence under constant temperature conditions, and the copper nanoparticles are obtained after the reaction is completed; Step 2, preparation of polyester: polyester monomers are dissolved in an organic solvent to obtain a monomer solution, and then a thermal initiator is added, and the polyester is obtained after polymerization is completed; Step 3, preparation of catalyst slurry: the copper nanoparticles and the polyester are added to a configuration solvent to disperse into a uniform catalyst slurry; Step 4, the catalyst slurry is dried to obtain the catalyst.

6. A polyester-modified copper nanoparticle catalyst slurry characterized by, The polyester-modified copper nanoparticles are the catalyst slurry in the preparation method of the polyester-modified copper nanoparticle catalyst of claim 5.

7. An electrode characterized by, The electrode comprises the polyester-modified copper nanoparticle catalyst of any one of claims 1-3 loaded on the surface of a conductive substrate, or is prepared from the polyester-modified copper nanoparticle catalyst slurry of claim 6.

8. A method of producing an electrode, characterized by The electrode comprises: The polyester-modified copper nanoparticle catalyst slurry of claim 6 is drop-coated on a conductive carrier, and after drying, the solvent in the catalyst slurry volatilizes, the catalyst is loaded on the surface of the conductive substrate, and the electrode is obtained.

9. A C 2+ product characterized in that, The C 2+ The product is produced by electrocatalytic carbon dioxide using the electrode of claim 7.

10. A C of claim 9 2+ Process for the preparation of a product, characterized in that, The above electrode is used as a working electrode to carry out an electrocatalytic carbon dioxide reduction reaction in a flow electrolytic cell to obtain the C 2+ product; wherein the C 2+ The product has a Faraday efficiency of 45-90% between current densities of 200-1000 mA / cm 2 between current densities of 200-1000 mA / cm

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