Foamed nickel supported nickel-cobalt metal organic framework catalyst, preparation method and application thereof

Abstract

The application belongs to the technical field of electrocatalytic materials, and provides a foam nickel loaded nickel cobalt metal organic framework catalyst, a preparation method and application thereof, and comprises the following steps: washing, drying, in sequence, the cut foam nickel under ultrasonic with nitric acid, ethanol and deionized water; uniformly mixing NiCl2·6H2O, CoCl2·6H2O and 2,5-thiophene dicarboxylic acid to obtain a mixed solution; dissolving the foam nickel and the mixed solution in a mixed solution of N,N-dimethylformamide and deionized water, and mixing and transferring in an ultrasonic machine to a polytetrafluoroethylene lined reaction kettle, and performing hydrothermal reaction; naturally cooling the reaction kettle, taking out the material, washing and vacuum drying. The preparation method is simple, the required raw materials and equipment are low in price, the production cost is low, can be applied to 1,4-cyclohexanedimethanol electro-oxidation to 1,4-cyclohexanedicarboxylic acid, the generated product is high in economic value, and is suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic materials technology, and particularly relates to nickel foam supported nickel-cobalt metal-organic framework catalysts, their preparation methods, and applications. Background Technology

[0002] With the overexploitation of fossil fuels and the aggravation of environmental pollution, there is an urgent need to develop and utilize clean energy. Among them, the electro-oxidation of small organic molecules can not only produce high-value-added chemicals at the anode, but also couple the hydrogen evolution reaction to produce high-purity hydrogen (H2), making it a research focus in the field of sustainable development.

[0003] Electrochemical oxidation of alcohols (AORs) is a typical electrochemical oxidation reaction of small organic molecules. It can produce valuable aldehydes, ketones, acids, and coupling products at the anode, while simultaneously generating hydrogen at the cathode. Therefore, replacing the anolyte oxidation reaction (OER) with alcohol electrochemical oxidation (AOR) in water electrolysis hydrogen production systems provides a highly valuable strategy for efficient hydrogen production. 1,4-Cyclohexanediethanol (CHDM) is an alicyclic diol, and its electrochemical oxidation is a research direction with significant industrial value. The electrochemical oxidation of 1,4-cyclohexanediethanol coupled with the hydrogen evolution reaction (HER) not only reduces the voltage required for hydrogen production and energy consumption but also produces high-value-added 1,4-cyclohexanedicarboxylic acid at the anode. Therefore, developing high-efficiency and stable transition metal catalysts (Ni, Co, etc.) for the electrochemical oxidation of 1,4-cyclohexanediethanol is of great significance.

[0004] 1,4-Cyclohexanedicarboxylic acid (CHDA) is an important alicyclic dicarboxylic acid with wide applications in high-performance polymers and fine chemicals. Currently, there are few methods for synthesizing CHDA, mainly through the hydrogenation of terephthalate, the hydrolysis of dimethyl 1,4-cyclohexanedicarboxylate, and other methods. Among these, the hydrolysis method, although requiring mild reaction conditions, is lengthy and time-consuming. The direct hydrogenation method, while shorter, requires high temperature and pressure conditions and demands high acid resistance and activity of the catalyst, often relying on expensive precious metal catalysts. Furthermore, the synthesis process is accompanied by problems such as low purity and severe environmental pollution. Electrochemical oxidation technology, on the other hand, offers mild reaction conditions, strong controllability, and no secondary pollution. It can directly prepare high-purity CHDA through the electrochemical oxidation of 1,4-cyclohexanediethanol (CHDM), providing a green new route for CHDA synthesis. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing nickel-cobalt metal-organic framework catalysts supported on nickel foam, in order to solve the problems mentioned in the background art.

[0006] The present invention is implemented as follows: a method for preparing a nickel-cobalt metal-organic framework catalyst supported on nickel foam includes the following steps:

[0007] (1) The cut nickel foam was washed and dried in turn with nitric acid, ethanol and deionized water under ultrasonic conditions.

[0008] (2) Mix NiCl2·6H2O, CoCl2·6H2O and 2,5-thiophene dicarboxylic acid evenly to obtain a mixed solution; dissolve the cleaned nickel foam and the mixed solution in a mixed solution of N,N-dimethylformamide and deionized water, and transfer it to a polytetrafluoroethylene-lined reactor in an ultrasonic machine for hydrothermal reaction. After the reaction is completed, wait for the reactor to cool naturally, take out the material, wash and vacuum dry it to obtain NiCo-MOF material.

[0009] Another objective of this invention is to provide a nickel foam-supported nickel-cobalt metal-organic framework catalyst, which is prepared using the above-described preparation method.

[0010] Another objective of this invention is to provide the application of a nickel foam-supported nickel-cobalt metal-organic framework catalyst in the electro-oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid.

[0011] The method for preparing the nickel-cobalt metal-organic framework (NiCo-MOF) catalyst supported on nickel foam provided in this invention is simple, requires inexpensive raw materials and equipment, and has low production costs. It can be applied to the electro-oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid, and the resulting product has high economic value and is suitable for large-scale production. Attached Figure Description

[0012] Figure 1 The XRD pattern of the NiCo-MOF-140 °C catalyst prepared in Example 1 of this invention is shown below.

[0013] Figure 2 The linear sweep voltammetry (LSV) curves of the samples prepared in Examples 1, 6, 7, 8 and Comparative Sample 1 of this invention as electrocatalysts for the electrochemical oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid are shown.

[0014] Figure 3 The cyclic voltammetry (CV) curve of the sample prepared in Example 1 of this invention in a mixed solution of 1 mol / L potassium hydroxide and 0.2 mol / L 1,4-cyclohexanediethanol is shown.

[0015] Figure 4 This is the cyclic voltammetry test curve for Comparative Example 1 of this invention;

[0016] Figure 5 The diagram shows the double-layer capacitance values ​​of Embodiment 1 and Comparative Example 1 of the present invention;

[0017] Figure 6 The voltage-time curves are obtained by testing the constant potential cycling stability of the samples prepared in Example 1 and Comparative Example 1 of this invention in the membrane electrode for the electro-oxidation reaction of 1,4-cyclohexanediethanol.

[0018] Figure 7 The Faraday efficiency, yield, and conversion of the samples prepared in Example 1 of this invention were measured at constant potentials of 1.46, 1.51, 1.56, 1.61, and 1.66 V vs. RHE. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0020] A nickel foam supported nickel-cobalt metal-organic framework (NiCo-MOF) catalyst, the preparation method of which includes the following steps:

[0021] (1) The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C;

[0022] (2) Dissolve 0~2 mmol NiCl2·6H2O, 0~2 mmol CoCl2·6H2O and 1~2 mmol 2,5-thiophene dicarboxylic acid (H2TDC) in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mix them evenly in an ultrasonic machine; then, transfer the cleaned nickel foam and the mixed solution to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 110~170 °C for 6~18 hours. After the reactor cools naturally, take out the material, wash it with deionized water and vacuum dry it at 60 °C for 12 h to obtain NiCo-MOF material.

[0023] The prepared nickel foam supported nickel-cobalt metal-organic framework catalyst was applied to the electrochemical oxidation of 1,4-cyclohexanediethanol;

[0024] Specifically, the steps include: setting up an H-type electrolytic cell as the electrochemical reaction cell, using a three-electrode system, with nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF) catalyst as the working electrode, Hg / HgO as the reference electrode, and a platinum sheet as the counter electrode. The anode and cathode electrolytes in the H-type cell are a 1 mol / L potassium hydroxide (KOH) and a 0.2 mol / L 1,4-cyclohexanediethanol mixed solution, and a 1 mol / L KOH solution, respectively. The applied potential during energization is 1.2-1.7 V compared to the reversible hydrogen electrode.

[0025] Alternatively, the following steps may be included: constructing a membrane electrode assembly in which a nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF) catalyst is used as the anode, a platinum-plated titanium felt is used as the cathode, and the electrolytes for the anode and cathode are a mixed solution of 1 mol / L potassium hydroxide (KOH) and 0.2 mol / L 1,4-cyclohexanediethanol and a 1 mol / L KOH solution, respectively, and the current applied during energization is 2A.

[0026] The specific implementation of the present invention will be described in detail below with reference to specific embodiments.

[0027] Example 1: A nickel foam supported nickel-cobalt metal-organic framework (NiCo-MOF-140 ℃) catalyst, the specific preparation method of which is as follows:

[0028] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-140 °C catalyst.

[0029] Example 2: A nickel foam supported nickel-cobalt metal-organic framework (NiCo-MOF-110 °C) catalyst, the specific preparation method of which is as follows:

[0030] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 110 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-110 °C catalyst.

[0031] Example 3: A nickel foam supported nickel-cobalt metal-organic framework (NiCo-MOF-170 ℃) catalyst, the specific preparation method of which is as follows:

[0032] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 170 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-170 °C catalyst.

[0033] Example 4: A nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF-6 h) catalyst, the preparation method of which is as follows:

[0034] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 6 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-6 h catalyst.

[0035] Example 5: A nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF-18h) catalyst, the specific preparation method of which is as follows:

[0036] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 18 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-18 h catalyst.

[0037] Example 6: A nickel foam supported nickel-cobalt metal-organic framework (NiCo(0:2)-MOF) catalyst, the preparation method of which is as follows:

[0038] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 2 mmol CoCl2·6H2O and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo(0:2)-MOF catalyst.

[0039] Example 7: A nickel foam supported nickel-cobalt metal-organic framework (NiCo(1:1)-MOF) catalyst, the specific preparation method of which is as follows:

[0040] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1 mmol NiCl2·6H2O, 1 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo(1:1)-MOF catalyst.

[0041] Example 8: A nickel foam supported nickel-cobalt metal-organic framework (NiCo(0.25:1.75)-MOF) catalyst, the specific preparation method of which is as follows:

[0042] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 0.25 mmol NiCl2·6H2O, 1.75 mmol CoCl2·6H2O, and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo(0.25:1.75)-MOF catalyst.

[0043] Example 9: A nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF-1.5 mM) catalyst, the specific preparation method of which is as follows:

[0044] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 1.5 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-1.5 mM catalyst.

[0045] Example 10: A nickel foam-supported nickel-cobalt metal-organic framework (NiCo-MOF-2 mM) catalyst, the preparation method of which is as follows:

[0046] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 1.75 mmol NiCl2·6H2O, 0.25 mmol CoCl2·6H2O, and 2 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the NiCo-MOF-2 mM catalyst.

[0047] Comparative Example 1: A nickel foam-supported nickel-cobalt metal-organic framework (Ni-MOF) catalyst, the specific preparation method of which is as follows:

[0048] The cut nickel foam was washed sequentially with 1 M nitric acid solution, ethanol, and deionized water under ultrasonication for 10 minutes, and then dried at 60 °C. 2 mmol NiCl2·6H2O and 1 mmol 2,5-thiophene dicarboxylic acid (H2TDC) were dissolved in a mixed solution of 10 mL N,N-dimethylformamide and 10 mL deionized water, and mixed thoroughly in an ultrasonic machine. Then, the cleaned nickel foam and the mixed solution were transferred to a polytetrafluoroethylene-lined reactor for hydrothermal reaction at 140 °C for 12 hours. After the reactor cooled naturally, the material was removed, washed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the Ni-MOF catalyst.

[0049] Performance testing:

[0050] The XRD pattern of the nickel foam-supported nickel-cobalt metal-organic framework NiCo-MOF-140 ℃ catalyst prepared in Example 1 is shown in the figure below. Figure 1 As shown;

[0051] The samples prepared in Examples 1, 6, 7, 8, and Comparative Example 1 were used as electrocatalysts to test their performance in the electrochemical oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid. Five samples were used as working electrodes, a platinum sheet as the counter electrode, and mercury / mercuric oxide (Hg / HgO) as the reference electrode. The applied potential during electrochemical workstation testing showed that it was 1.2-1.6 V higher than that of the reversible hydrogen electrode. Figure 2 The LSV curve shown is from Figure 2 It can be seen that the nickel-cobalt metal-organic framework NiCo-MOF-140 ℃ catalyst supported on nickel foam, in a mixed solution of 1 mol / L potassium hydroxide and 0.2 mol / L 1,4-cyclohexanediethanol, requires only 1.346 V (relative to the reversible hydrogen electrode) to achieve 100 mA / cm². 2 The current density is used to drive the electro-oxidation reaction of 1,4-cyclohexanediethanol, and it reaches 500 mA / cm². 2 The current density required is only 1.45V (relative to a standard hydrogen electrode);

[0052] The samples prepared in Example 1 and Comparative Example 1 were subjected to cyclic voltammetry tests, and the double-layer capacitance was calculated. The cyclic voltammetry curve of Example 1 is shown below. Figure 3 As shown, the results of the double-layer capacitance values ​​are as follows: Figure 5 As shown, the cyclic voltammetry curve of Comparative Example 1 is as follows: Figure 4 As shown, the results of the double-layer capacitance values ​​are as follows: Figure 5 As shown;

[0053] The samples prepared in Example 1 and Comparative Example 1 were used in membrane electrodes for constant potential cycling stability testing of the electro-oxidation reaction of 1,4-cyclohexanediethanol. The obtained voltage-time curves are shown below. Figure 6 As shown;

[0054] The sample prepared in Example 1 was used as an electrocatalyst material, and constant potential tests (potentials of 1.46, 1.51, 1.56, 1.61, and 1.66 V vs. RHE) were conducted in an H-type cell to examine its Faradaic efficiency, CHDM conversion, and CHDA yield in the electrochemical oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid. The results are as follows: Figure 7 As shown, from Figure 7 As can be seen, when the applied constant potential is 1.61 V vs. RHE, the Faraday efficiency of the reaction reaches a maximum of 94.8%, the CHDM conversion reaches a maximum of 95.5%, and the CHDA yield reaches a maximum of 94.9%.

[0055] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a nickel-cobalt metal-organic framework catalyst supported on nickel foam, characterized in that, Includes the following steps: (1) The cut nickel foam was washed and dried in turn with nitric acid, ethanol and deionized water under ultrasonic conditions. (2) Mix NiCl2·6H2O, CoCl2·6H2O and 2,5-thiophene dicarboxylic acid evenly to obtain a mixed solution; dissolve the cleaned nickel foam and the mixed solution in a mixed solution of N,N-dimethylformamide and deionized water, and transfer it to a polytetrafluoroethylene-lined reactor in an ultrasonic machine for hydrothermal reaction. After the reaction is completed, wait for the reactor to cool naturally, take out the material, wash and vacuum dry it to obtain NiCo-MOF material.

2. The method for preparing the nickel-cobalt metal-organic framework catalyst supported on nickel foam according to claim 1, characterized in that, In step (1), the concentration of nitric acid is 1-1.5 mol / L, and the ultrasonic washing time is 10-20 min.

3. The method for preparing the nickel-cobalt metal-organic framework catalyst supported on nickel foam according to claim 1, characterized in that, In step (2), the molar ratio of NiCl2·6H2O, CoCl2·6H2O and 2,5-thiophene dicarboxylic acid is 0~2:0~2:1~2.

4. The method for preparing the nickel-cobalt metal-organic framework catalyst supported on nickel foam according to claim 1, characterized in that, In step (2), the volume ratio of N,N-dimethylformamide to deionized water is 1:

1.

5. The method for preparing the nickel-cobalt metal-organic framework catalyst supported on nickel foam according to claim 1, characterized in that, In step (2), the temperature of the hydrothermal reaction is 110~170 ℃ and the time is 6-18 h.

6. A nickel foam-supported nickel-cobalt metal-organic framework catalyst, characterized in that, It is prepared using the preparation method described in any one of claims 1-5.

7. The application of the nickel foam-supported nickel-cobalt metal-organic framework catalyst as described in claim 6 in the electro-oxidation of 1,4-cyclohexanediethanol to 1,4-cyclohexanedicarboxylic acid.

8. The application according to claim 7, characterized in that, Includes the following steps: Nickel foam supported nickel-cobalt metal-organic framework catalyst was placed in an electrochemical reaction cell. Using 1,4-cyclohexanediethanol as raw material, 1,4-cyclohexanedicarboxylic acid was generated on the surface of the working electrode under the influence of electricity. The electrochemical reaction cell is an H-type cell, employing a three-electrode system. The nickel-cobalt metal-organic framework catalyst supported on nickel foam is used as the anode catalyst, the Pt sheet is used as the cathode electrocatalyst, and the reference electrode is an Hg / HgO electrode. The anode electrolyte in the H-type cell is a mixed solution of potassium hydroxide and 1,4-cyclohexanediethanol, and the cathode electrolyte is a potassium hydroxide solution. The electro-oxidation reaction of 1,4-cyclohexanediethanol is driven by an electric current.

9. The application according to claim 7, characterized in that, The potential applied during energization is 1.2~1.7V relative to the reversible hydrogen electrode.

10. The application according to claim 7, characterized in that, Includes the following steps: A membrane electrode assembly was constructed to perform the electrochemical oxidation of 1,4-cyclohexanediethanol under constant current; In the membrane electrode assembly, a nickel-cobalt metal-organic framework catalyst supported on nickel foam is used as the anode material, a platinum-plated titanium felt is used as the cathode material, the anode electrolyte is a mixed solution of potassium hydroxide and 1,4-cyclohexanediethanol, the cathode electrolyte is a potassium hydroxide solution, and the applied current is 2A.

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