A copper-nickel alloy catalytic electrode, a preparation method and application thereof

Abstract

The application provides a copper-nickel alloy catalytic electrode and a preparation method and application thereof. The copper-nickel alloy catalytic electrode comprises a nickel foam substrate and a copper-nickel alloy vertically loaded on the surface of the nickel foam substrate, the molecular formula of the copper-nickel alloy is Cu 0.81 Ni 0.19 , and the copper-nickel alloy is a nanostructure with a dendritic morphology. The preparation method comprises the following steps: adding copper sulfate, nickel sulfate and ammonium sulfate into water, stirring uniformly to obtain an electrolyte; taking the nickel foam substrate as a working electrode, a saturated silver-silver chloride electrode as a reference electrode, a platinum sheet or a graphite rod electrode as a counter electrode, applying a constant current density to the working electrode to obtain a preset electrode; alternately cleaning the preset electrode with ethanol and distilled water, and vacuum drying to obtain the copper-nickel alloy catalytic electrode. The copper-nickel alloy catalytic electrode prepared by the application has a dendritic morphology, rich active sites and a high specific surface area, and has excellent catalytic activity and stability in the hydrogen production by the electro-catalytic coupling hydrogen evolution reaction of cyclohexanone synthesis adipic acid.

Description

Technical Field

[0001] This invention relates to the fields of nanomaterial synthesis and electrocatalysis, specifically to a copper-nickel alloy catalytic electrode, its preparation method, and its application. Background Technology

[0002] In the field of electrocatalysis, non-precious metals such as iron, cobalt, nickel, and copper are valued for their abundant reserves, low cost, and good corrosion resistance. Nickel-based and copper-based materials, in particular, are not only abundant but also have easily tunable electronic structures, playing an important role in the synthesis of electrocatalysts.

[0003] Traditional methods for preparing nickel-copper based alloys, such as co-reduction, mechanical ball milling, pyrolysis reduction, and thermal diffusion, while successfully producing alloy materials, are often time-consuming and costly, hindering large-scale production. To address this issue, electrodeposition technology has emerged as an effective alternative. By selecting a suitable working electrode and an electrolyte containing a soluble metal salt, and applying a specific current, alloy catalysts can be deposited quickly and easily on the substrate material. However, further technological improvements are still needed to prepare three-dimensional alloy catalytic electrodes with high loading capacity and good structural stability.

[0004] Adipic acid is a key industrial raw material in chemical production processes, widely used in the production of nylon-66, polyurethane, and plasticizers. Traditionally, adipic acid production relies on a thermocatalytic reaction using concentrated nitric acid as an oxidant under high temperature and pressure. This process is not only energy-intensive but also generates exhaust gases that severely pollute the environment. To achieve a more environmentally friendly production method, the electrocatalytic oxidation of cyclohexanone / cyclohexanol to synthesize adipic acid has emerged. This method uses water as an oxidant, enabling efficient and clean production of adipic acid. During the electrocatalytic process, nickel-based materials form NiOOH during oxidation, which is the key active site for the oxidation of cyclohexanone to adipic acid. However, the utilization efficiency of nickel-based materials in the electrocatalytic cathode reaction still needs improvement. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] To address the shortcomings of existing technologies, this invention provides a copper-nickel alloy catalytic electrode, its preparation method, and its application, thus solving the problems mentioned in the background section.

[0007] (II) Technical Solution

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] According to a first aspect of the present invention, a copper-nickel alloy catalytic electrode is provided, comprising a nickel foam substrate and a copper-nickel alloy vertically loaded on the surface of the nickel foam substrate, the copper-nickel alloy having the molecular formula Cu. 0.81 Ni 0.19 The copper-nickel alloy has a dendritic nanostructure.

[0010] The copper-nickel alloy catalytic electrode of the present invention has a high specific surface area morphology generated in situ on the surface of nickel foam, and has good stability, exhibiting excellent catalytic activity during catalytic synthesis.

[0011] Preferably, the length of the copper-nickel alloy catalytic electrode is 1-2 cm, and the width of the copper-nickel alloy catalytic electrode is 1-2 cm.

[0012] According to a second aspect of the present invention, a method for preparing a copper-nickel alloy catalytic electrode is provided, comprising the following steps:

[0013] a) Add copper sulfate, nickel sulfate and ammonium sulfate to water and stir until homogeneous to obtain an electrolyte;

[0014] b) Using a nickel foam substrate as the working electrode, a saturated silver silver chloride electrode as the reference electrode, and a platinum sheet or graphite rod electrode as the counter electrode, the working electrode, reference electrode, and counter electrode are placed in the electrolyte, and a constant current density is applied to the working electrode to obtain a copper-nickel alloy pre-positioned electrode.

[0015] c) The copper-nickel alloy pre-placed electrode is alternately cleaned with ethanol and distilled water and then vacuum dried to obtain the copper-nickel alloy catalytic electrode.

[0016] This invention employs a simple and rapid electrodeposition synthesis method to prepare a self-supporting three-dimensional copper-nickel alloy catalyst in one step. Ammonium sulfate is added to the electrolyte, which not only enhances conductivity and complexation during the electrodeposition process, but also effectively enhances the corrosion resistance of the coating and maintains the pH of the electrolyte. Applying a certain negative current density to the working electrode reduces copper and nickel ions on the electrode surface to form an alloy with high loading capacity and excellent stability.

[0017] Preferably, in step a), the concentration of copper sulfate in the electrolyte is 12.5–37.5 mM;

[0018] The concentration of nickel sulfate in the electrolyte is 12.5–37.5 mM;

[0019] The concentration of ammonium sulfate is 50–60 mM.

[0020] More preferably, the molar ratio of nickel sulfate to copper sulfate in the electrolyte is 1:1.5 to 2;

[0021] The concentration of the ammonium sulfate is 60 mM.

[0022] Preferably, in step b), the constant current density applied to the working electrode is -150 to -50 mA cm⁻¹. -2 ;

[0023] The constant current density is applied for 2 to 15 minutes.

[0024] More preferably, in step b), the constant current density applied to the working electrode is -100 mA cm⁻¹. -2 ;

[0025] The constant current density was applied for 10 minutes.

[0026] Preferably, in step c), the alternating cleaning is performed 3 to 5 times;

[0027] The vacuum drying temperature is 80–100°C.

[0028] According to a third aspect of the present invention, a copper-nickel alloy catalytic electrode or a copper-nickel alloy catalytic electrode prepared according to the above preparation method is used in the electrocatalytic synthesis of cyclohexanone into adipic acid coupled with hydrogen evolution reaction to produce hydrogen.

[0029] (III) Beneficial Effects

[0030] This invention provides a copper-nickel alloy catalytic electrode, its preparation method, and its application. It offers the following advantages:

[0031] (1) The copper-nickel alloy catalytic electrode provided by this solution is a copper-nickel alloy vertically loaded on a foamed nickel substrate and has a dendritic morphology. It has abundant active sites and a high specific surface area, thus exhibiting excellent catalytic activity and stability. In addition, the copper-nickel alloy catalytic electrode of this invention can be quickly assembled into an electrode device for application without any conductive materials or auxiliary adhesive materials.

[0032] (2) The method for preparing a copper-nickel alloy catalytic electrode provided in this scheme firstly prepares an electrolyte. By adding ammonium sulfate to the electrolyte, the conductivity, complexation and corrosion resistance of the electrolyte are improved, and the pH of the electrolyte is effectively maintained. During the electrodeposition process, a certain negative current density is applied to the working electrode, so that copper ions and nickel ions are reduced on the electrode surface to form an alloy with high loading and excellent stability.

[0033] (3) The method for preparing a copper-nickel alloy catalytic electrode provided in this scheme is simple and convenient. The electrodeposition equipment has a simple structure, the chemical raw materials used are common and easy to obtain, the products are easy to collect, and it can be mass-produced on a large scale.

[0034] (4) The application of a copper-nickel alloy catalytic electrode provided in this solution is that, while leveraging the high efficiency and clean production of adipic acid from the original nickel-based materials, the copper-nickel alloy catalytic electrode can also couple the production of green hydrogen energy, thereby improving the utilization rate of the cathode reaction. In addition, it also has excellent working stability. Attached Figure Description

[0035] Figure 1 A process flow diagram of a copper-nickel alloy catalytic electrode provided by the present invention;

[0036] Figure 2 XRD patterns of a copper-nickel alloy catalytic electrode prepared according to the present invention are shown in Figure 1. Figure 2 shows the XRD pattern of the copper-nickel alloy catalytic electrode prepared in Example 1; Figure 3 shows the XRD pattern of the Ni sample prepared in Comparative Example 1; and Figure 4 shows the XRD pattern of the Cu-CuO sample prepared in Comparative Example 2.

[0037] Figure 3 The images shown are scanning electron microscope (SEM) images of a copper-nickel alloy catalytic electrode prepared according to the present invention. Image a is a 2 μm SEM image of the copper-nickel alloy catalytic electrode prepared in Example 1; image b is a 2 μm SEM image of the Ni sample prepared in Comparative Example 1; image c is a 2 μm SEM image of the Cu-CuO sample prepared in Comparative Example 2; image d is a 200 nm SEM image of the copper-nickel alloy catalytic electrode prepared in Example 1; image e is a 200 nm SEM image of the Ni sample prepared in Comparative Example 1; and image f is a 200 nm SEM image of the Cu-CuO sample prepared in Comparative Example 2.

[0038] Figure 4 Cu prepared in Example 1 of this invention 0.81 Ni 0.19 XPS spectra of the Cu-CuO / NF catalytic electrode, the Ni / NF catalytic electrode prepared in Comparative Example 1, and the Cu-CuO / NF catalytic electrode prepared in Comparative Example 2, where Figure a is the XPS spectrum of Cu 2p; Figure b is the XPS spectrum of Ni 2p.

[0039] Figure 5 The performance of the catalytic electrodes prepared in Example 1, Comparative Example 1 and Comparative Example 2 of this invention was tested under alkaline conditions of 1M KOH. Figure a shows the linear voltammetric curves of the hydrogen evolution reaction (HER) of the catalytic electrodes prepared in Example 1, Comparative Example 1 and Comparative Example 2; Figure b shows the hydrogen production Faraday efficiency of the catalytic electrode prepared in Example 1 under different time tests.

[0040] Figure 6 Cu prepared in Example 1 of this invention 0.81 Ni 0.19The HER chronovoltage curve obtained by electrochemical three-electrode testing of the / NF catalytic electrode under alkaline conditions of 1M KOH;

[0041] Figure 7 The image shows the linear voltammetric curves of the copper-nickel alloy catalytic electrode synthesized under different ratios of copper and nickel salts according to the present invention, measured under alkaline conditions of 1 MKOH.

[0042] Figure 8 Figure a shows the linear voltammetric curves of cyclohexanone oxidation (COR) tested in 1M KOH and 0.4M cyclohexanone solution for the catalytic electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2; Figure b shows the yield of adipic acid produced by oxidation in 1M KOH and 0.4M cyclohexanone solution for the catalytic electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2; Figure c shows the Faradaic efficiency of adipic acid produced by oxidation in 1M KOH and 0.4M cyclohexanone solution for the catalytic electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2.

[0043] Figure 9 Figure a shows the Cu prepared in Example 1. 0.81 Ni 0.19 The conversion rate of cyclohexanone and the yield of oxalic acid in the oxidation of cyclohexanone (COR) to adipic acid were tested at different reaction times using an / NF catalytic electrode in 1M KOH and 0.4M cyclohexanone solution; Figure b shows the Cu prepared in Example 1. 0.81 Ni 0.19 1H NMR spectrum of cyclohexanone oxidation (COR) to adipic acid, tested on an NF catalytic electrode in 1M KOH and 0.4M cyclohexanone solution. 1 H NMR);

[0044] Figure 10 Cu prepared in Example 1 of this invention 0.81 Ni 0.19 The yield and faradaic efficiency stability of cyclohexanone oxidation (COR) to adipic acid were tested five times consecutively without changing the catalyst using an / NF catalytic electrode in 1M KOH and 0.4M cyclohexanone solution.

[0045] Figure 11 Cu prepared in Example 1 of this invention 0.81 Ni 0.19 The performance of the NF catalytic electrode in a flow electrolyzer was tested for the total decomposition system of KA oil oxidation and hydrogen evolution in a mixed solution of 1M KOH and 0.4M cyclohexanone / cyclohexanol (KA oil). Figure a shows the total decomposition performance of oxidation and hydrogen evolution, Figure b shows the Faradaic efficiency and yield of the total decomposition system in producing adipic acid at different current densities, and Figure c shows the Faradaic efficiency and yield of the total decomposition system in producing hydrogen at different current densities.

[0046] Figure 12 Cu prepared in Example 1 of this invention 0.81 Ni 0.19 The NF catalytic electrode was used to test the total decomposition system of KA oil oxidation and hydrogen evolution reaction in a fluid electrolyzer at 100 mA / cm² in a mixed solution of 1 M KOH and 0.4 M cyclohexanone / cyclohexanol (KA oil). -2 The stability curve at the current density. Detailed Implementation

[0047] To better illustrate the content of this invention, the following description is provided in conjunction with specific embodiments.

[0048] Example 1

[0049] A Cu 0.81 Ni 0.19 The preparation method and process flow of the / NF catalytic electrode are as follows: Figure 1 As shown:

[0050] Step 1: Prepare a mixed solution containing 0.03M nickel sulfate hexahydrate, 0.02M copper sulfate and 0.06M sulfuric acid to obtain a light blue electrolyte;

[0051] Step 2: Select a 1×2cm piece 2 A three-electrode electrolytic cell was constructed using nickel foam as the working electrode, saturated silver chloride as the reference electrode, a platinum sheet as the counter electrode, and the mixed solution from step 1 as the electrode electrolyte. A -100 mA cm⁻¹ was applied to the working electrode. -2 At a constant current density, the surface of the nickel foam substrate quickly turns black. After applying a constant current density for 600 seconds, the black Cu... 0.81 Ni 0.19 The alloy will tightly cover the surface of the nickel foam substrate, resulting in a copper-nickel alloy pre-electrode;

[0052] Step 3: Clean the copper-nickel alloy pre-electrode from Step 2 with alternating ultrasonic cleaning of ethanol and distilled water for 5 minutes to remove residues on the surface of the copper-nickel alloy pre-electrode. Repeat this process three times to remove the electrode and place it in a vacuum oven to dry at 80°C for 30 minutes to obtain the copper-nickel alloy catalytic electrode.

[0053] Example 2

[0054] The preparation method of this embodiment is the same as that of Example 1, except that in step 1, the molar ratio of nickel sulfate hexahydrate and copper sulfate in the electrolyte is 3:1.

[0055] Example 3

[0056] The preparation method of this embodiment is the same as that of Example 1, except that in step 1, the molar ratio of nickel sulfate hexahydrate and copper sulfate in the electrolyte is 1:1.

[0057] Example 4

[0058] The preparation method of this embodiment is the same as that of Example 1, except that in step 1, the molar ratio of nickel sulfate hexahydrate and copper sulfate in the electrolyte is 1:1.5.

[0059] Example 5

[0060] The preparation method of this embodiment is the same as that of Example 1, except that in step 1, the molar ratio of nickel sulfate hexahydrate and copper sulfate in the electrolyte is 1:3.

[0061] Comparative Example 1

[0062] A method for preparing a Ni / NF catalytic electrode includes the following steps:

[0063] Step 1: Prepare a mixed solution of 0.03M nickel sulfate hexahydrate and 0.06M ammonium sulfate to obtain a light green electrolyte;

[0064] Step 2: Select a 1×2cm piece 2 A three-electrode electrolytic cell was constructed using nickel foam as the working electrode, saturated silver chloride as the reference electrode, a platinum sheet as the counter electrode, and the mixed solution from step 1 as the electrode electrolyte. A -100 mA cm⁻¹ was applied to the working electrode. -2 At a constant current density, the surface of the nickel foam substrate will quickly turn black. After applying a constant current density for 600 seconds, the black Ni catalyst will tightly cover the surface of the nickel foam substrate, resulting in a Ni pre-electrode.

[0065] Step 3: Clean the Ni pre-electrode from Step 2 with alternating ultrasonic cleaning of ethanol and distilled water for 5 minutes to remove residues on the surface of the Ni pre-electrode. Repeat this process three times to remove the electrode and place it in a vacuum oven to dry at 80°C for 30 minutes to obtain the Ni / NF catalytic electrode.

[0066] Comparative Example 2

[0067] A method for preparing a Cu-CuO / NF catalytic electrode includes the following steps:

[0068] Step 1: Prepare a mixed aqueous solution of 0.02M copper sulfate and 0.06M ammonium sulfate to obtain a light blue electrolyte;

[0069] Step 2: Select a 1×2cm piece 2A three-electrode electrolytic cell was constructed using nickel foam as the working electrode, saturated silver chloride as the reference electrode, a platinum sheet as the counter electrode, and the mixed solution from step 1 as the electrode electrolyte. A -100 mA cm⁻¹ was applied to the working electrode. -2 At a constant current density, the surface of the nickel foam substrate will quickly turn black. After applying a constant current density for 600 seconds, the brown Cu-CuO catalyst will tightly cover the surface of the nickel foam substrate, resulting in a Cu-CuO pre-electrode.

[0070] Step 3: Clean the Cu-CuO pre-electrode from Step 2 with alternating ultrasonic cleaning of ethanol and distilled water for 5 minutes to remove residues on the surface of the Cu-CuO pre-electrode. Repeat this process three times to remove the electrode and place it in a vacuum oven to dry at 80°C for 30 minutes to obtain the Cu-CuO catalytic electrode.

[0071] Comparative Example 3

[0072] A method for preparing a copper-nickel alloy catalytic electrode includes the following steps:

[0073] Step 1: Prepare a mixed solution containing 0.05M nickel sulfate hexahydrate, 0.01M copper sulfate and 0.06M sulfuric acid to obtain a light blue electrolyte.

[0074] Step 2: Select a 1×2cm piece 2 A three-electrode electrolytic cell was constructed using nickel foam as the working electrode, saturated silver chloride as the reference electrode, a platinum sheet as the counter electrode, and the mixed solution from step 1 as the electrode electrolyte. A -100 mA cm⁻¹ was applied to the working electrode. -2 At a constant current density, the surface of the nickel foam substrate will quickly turn black. After applying a constant current density for 600 seconds, the black copper-nickel alloy will tightly cover the surface of the nickel foam substrate, resulting in a copper-nickel alloy pre-electrode.

[0075] Step 3: Clean the copper-nickel alloy pre-electrode from Step 2 with alternating ultrasonic cleaning of ethanol and distilled water for 5 minutes to remove residues on the surface of the copper-nickel alloy pre-electrode. Repeat this process three times to remove the electrode and place it in a vacuum oven to dry at 80°C for 30 minutes to obtain the copper-nickel alloy catalytic electrode.

[0076] Characterization and performance testing:

[0077] XRD analysis was performed on Example 1, Comparative Example 1, and Comparative Example 2, respectively. Figure 2 As shown in Figures a to c, the catalytic materials on the electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2 all conform to Cu 0.81 Ni 0.19 The phases of Ni and Cu-CuO.

[0078] SEM analysis was performed on Example 1, Comparative Example 1, and Comparative Example 2, respectively. Figure 3 As shown, by comparing a to c and d to e, it can be seen that the Cu of the present invention 0.81 Ni 0.19 The material is evenly distributed on the surface of the nickel foam substrate. The uniform distribution and dendritic shape present numerous pores, which facilitates full contact with the substrate during the reaction process, thereby exposing more catalytic active sites and promoting the occurrence of catalytic reactions.

[0079] X-ray photoelectron spectroscopy (XPS) tests were performed on samples from Example 1, Comparative Example 1, and Comparative Example 2, respectively. Figure 4 As shown in Figure a, which is the XPS spectrum data of Cu 2p and Figure b, which is the XPS spectrum data of Ni 2p, it can be seen that the catalytic electrode prepared in Example 1 contains both Cu and Ni elements.

[0080] The linear voltammetric curves of the hydrogen evolution reaction (HER) were tested under alkaline conditions of 1M KOH using the catalytic electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2, respectively. Figure 5 As shown in Figure a, the Cu prepared in Example 1... 0.81 Ni 0.19 Catalytic electrode at -100mA cm -2 At a current density of 162 mV, the Cu electrode prepared in Example 1 exhibits an overpotential significantly higher than that prepared in Comparative Examples 1 and 2, demonstrating significantly superior catalytic performance. As shown in Figure b, the Cu electrode prepared in Example 1... 0.81 Ni 0.19 The Faraday efficiency of hydrogen production by the catalytic electrode at different times is higher than 90%, which proves that the catalytic electrode prepared in Example 1 has excellent hydrogen production performance.

[0081] Figure 6 Cu prepared in Example 1 0.81 Ni 0.19 The catalytic electrode was used with a three-electrode system under alkaline conditions of 1M KOH at -50 mA cm⁻¹. -2 The HER chronovoltaic curves obtained after 30 hours of electrolysis at a constant current density demonstrate that the Cu prepared in Example 1... 0.81 Ni 0.19 The catalytic electrode exhibits good stability and can be applied to the actual industrial production of hydrogen.

[0082] Figure 7 The HER linear voltammetry curves of nickel-copper alloy catalytic electrodes prepared by deposition in electrolytes containing nickel and copper salts at different ratios in Examples 1 to 5 and Comparative Example 3, tested under alkaline conditions of 1M KOH, are shown below. Figure 7It can be seen that the hydrogen evolution performance of the material deposited with nickel salt and copper salt at a ratio of 1.5:1 is the best. In Comparative Example 3, the addition of excessive nickel salt significantly reduced the hydrogen evolution performance.

[0083] The catalytic electrodes prepared in Example 1, Comparative Example 1, and Comparative Example 2 were tested for cyclohexanone oxidation (COR) performance, yield, and Faradaic efficiency in 1M KOH and 0.4M cyclohexanone solutions, respectively. Figure 8 As shown in Figure a, the Cu prepared in Example 1... 0.81 Ni 0.19 The Cu / NF catalytic electrode exhibits excellent catalytic performance for cyclohexanone oxidation, significantly outperforming the catalytic performance of Ni / NF and Cu-CuO / NF electrode materials. As shown in Figures b and c, the Cu prepared in Example 1… 0.81 Ni 0.19 The / NF catalytic electrode exhibits excellent yield and Faradaic efficiency in the electrocatalytic oxidation of cyclohexanone to adipic acid, achieving an efficiency of 92% at 1.45V.

[0084] Test Example 1 prepared Cu 0.81 Ni 0.19 Data on the conversion of cyclohexanone and the yield of adipic acid synthesis at different reaction times using the / NF catalytic electrode in 1M KOH and 0.4M cyclohexanone solutions, along with the corresponding 1H NMR spectra, are as follows: Figure 9 As shown in Figures a and b, the yield of adipic acid continuously increases with increasing electrolysis time, reaching a maximum yield of 80% after 10 hours. This demonstrates that the Cu prepared in Example 1... 0.81 Ni 0.19 / NF catalytic electrodes have excellent industrial value in the synthesis of adipic acid.

[0085] Cu prepared in the test examples 0.81 Ni 0.19 The stability graph of the yield and faradaic efficiency of the cyclohexanone oxidation (COR) to adipic acid synthesis using an / NF catalytic electrode in 1M KOH and 0.4M cyclohexanone solution was obtained by continuous testing for 5 cycles without catalyst replacement. Figure 10 As shown, the Cu prepared in this embodiment... 0.81 Ni 0.19 The / NF catalytic electrode exhibits excellent adipic acid yield and Faraday efficiency stability.

[0086] Test Example 1 prepared Cu 0.81 Ni 0.19 The performance of the / NF catalytic electrode in a fluid electrolyzer was tested in a mixed solution of 1M KOH and 0.4M cyclohexanone / cyclohexanol (KA oil) to measure the total decomposition system of KA oil oxidation and hydrogen evolution. (See graph for example.) Figure 11As shown in Figure a, it can be seen that the Cu prepared in Example 1... 0.81 Ni 0.19 The / NF catalytic electrode exhibits excellent total decomposition performance of KA oil oxidation coupled with hydrogen evolution. As shown in Figures b and c, the Cu prepared in Example 1... 0.81 Ni 0.19 / NF catalytic electrode at 25, 50, 75, 100, 125 mA cm -2 The Faraday efficiency for producing hydrogen and adipic acid exceeds 90%.

[0087] Test Example 1 prepared Cu 0.81 Ni 0.19 The total decomposition system of KA oil oxidation and hydrogen evolution reaction was tested in a flow electrolyzer using a / NF catalytic electrode in a mixed solution of 1M KOH and 0.4M cyclohexanone / cycloethanol (KA oil) at 100 mA cm⁻¹. -2 The stability test curves under current density, such as Figure 12 As shown, Cu prepared in Example 1 0.81 Ni 0.19 The / NF catalytic electrode exhibits excellent long-term operational stability.

[0088] The copper-nickel alloy catalytic electrode prepared by this invention has a dendritic morphology with uniform distribution and abundant active sites and specific surface area. When applied to the electrosynthesis of adipic acid coupled with hydrogen production, the catalytic electrode prepared by this invention has a high adipic acid yield, excellent hydrogen evolution catalytic activity and good stability, and can be practically applied in equipment for the production of adipic acid and hydrogen.

[0089] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A copper-nickel alloy catalytic electrode, characterized in that: It includes a nickel foam substrate and a copper-nickel alloy with the molecular formula Cu, which is vertically loaded on the surface of the nickel foam substrate. 0.81 Ni 0.19 The copper-nickel alloy has a dendritic nanostructure. The preparation method of the copper-nickel alloy catalytic electrode is as follows: a) Add copper sulfate, nickel sulfate and ammonium sulfate to water and stir until homogeneous to obtain an electrolyte; b) Using a nickel foam substrate as the working electrode, a saturated silver silver chloride electrode as the reference electrode, and a platinum sheet or graphite rod electrode as the counter electrode, the working electrode, reference electrode, and counter electrode are placed in the electrolyte, and a constant current density is applied to the working electrode to obtain a copper-nickel alloy pre-positioned electrode. c) The copper-nickel alloy pre-placed electrode is alternately cleaned with ethanol and distilled water and then vacuum dried to obtain the copper-nickel alloy catalytic electrode; In step a), the concentration of copper sulfate in the electrolyte is 12.5~37.5mM; The concentration of nickel sulfate in the electrolyte is 12.5~37.5 mM; The concentration of the ammonium sulfate is 50-60 mM; The molar ratio of nickel sulfate to copper sulfate in the electrolyte is 1:1.5~2.

2. The copper-nickel alloy catalytic electrode according to claim 1, characterized in that: The copper-nickel alloy catalytic electrode has a length of 1-2 cm and a width of 1-2 cm.

3. The copper-nickel alloy catalytic electrode according to claim 1, characterized in that: In step b), the constant current density applied to the working electrode is -150 to -50 mA cm⁻¹. -2 ; The constant current density is applied for 2 to 15 minutes.

4. The method for preparing a copper-nickel alloy catalytic electrode according to claim 3, characterized in that: In step b), the constant current density applied to the working electrode is -100 mA cm⁻¹. -2 ; The constant current density was applied for 10 minutes.

5. The method for preparing a copper-nickel alloy catalytic electrode according to claim 1, characterized in that: In step c), the alternating cleaning is performed 3 to 5 times; The vacuum drying temperature is 80~100℃.

6. The application of the copper-nickel alloy catalytic electrode according to any one of claims 1 to 5 in the production of hydrogen gas by electrocatalytic synthesis of adipic acid from cyclohexanone coupled with hydrogen evolution reaction.

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