A method for preparing a copper-based electrode based on electroplating of a complex copper solution and its application

Abstract

The present invention discloses a method for preparing a copper-based electrode based on electroplating of a complex copper solution and its application. The method for preparing a copper-based electrode based on electroplating of a complex copper solution comprises the following steps: (1) loading boron nitride powder on a conductive substrate to prepare a boron nitride electrode; (2) placing the boron nitride electrode in a complex copper solution to perform an electroplating reaction, electroplating copper on the surface of the boron nitride to prepare a copper-based electrode. The present invention can improve the effect of electroplating copper, thereby improving the effect of electrochemical reduction to remove florfenicol.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochemistry, and in particular relates to a method for preparing a copper-based electrode based on electro-deposition of a complex copper solution and an application thereof. Background Art

[0002] In December 2022, the Ministry of Ecology and Environment issued a list of new pollutants under key control (2023 edition), which listed antibiotics as control objects. The main hazard of antibiotics is that they can produce drug-resistant bacteria and resistance genes, which can cause relatively serious damage to the ecological environment and human health. In particular, antibiotics containing halogen atoms are difficult to remove by conventional water treatment methods due to their high toxicity and stable carbon-halogen bonds. They are one of the difficult types of antibiotics to treat, such as florfenicol. At present, electrochemical reduction technology, one of the cutting-edge new technologies, has shown good results in the treatment of halogen-containing antibiotics. This technology mainly produces atomic hydrogen through the electrolysis of water, reduces and removes halogen atoms in antibiotics, removes resistance genes, reduces toxicity, and enables them to be degraded by conventional water treatment methods. It has the characteristics of green, low-carbon, high efficiency, simple operation, small footprint and no secondary pollution risk, and is widely used in the treatment of various antibiotic-containing wastewaters. However, this technology still has the problem of how to develop efficient, economical and stable electrode materials, which is very necessary for the practical application of this technology.

[0003] The materials commonly used in electrochemical reduction technology are precious metal palladium-based materials. Palladium-based materials have the ability to efficiently produce atomic hydrogen, can effectively remove halogen atoms in antibiotics, remove resistance genes, reduce the toxicity of antibiotics, and make them easy to be treated by conventional water treatment technology. However, the raw materials for preparing palladium-based electrodes are expensive, making it difficult to use them in actual wastewater treatment. Some transition metal materials have shown certain effects in electrochemical reduction reactions, such as cobalt and copper. The morphology of the material and the content of the metal have a great influence on the effect of electrochemical reduction. Reasonable design of the catalyst can effectively improve the electrochemical reduction activity of the electrode.

[0004] Reasonable preparation of copper-based materials is one of the methods to improve the electrochemical reduction activity of electrodes. Conventional methods for preparing copper-based electrodes are complex and costly. In addition, with the increasing demand for new energy batteries, a large amount of copper-containing complex wastewater is also generated during the production of batteries. Recycling copper in wastewater to prepare electrodes can greatly reduce the cost of manufacturing copper-based material electrodes, while solving the environmental pollution problem caused by copper as a heavy metal. However, there is currently a lack of reliable technology for using copper-containing complex wastewater to prepare copper-based electrode materials for the treatment of new pollutants such as antibiotics. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a method for preparing a copper-based electrode based on electroplating of a complex copper solution and its application, which can improve the effect of depositing copper, thereby improving the effect of electrochemical reduction to remove florfenicol.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a copper-based electrode based on electroplating of a complex copper solution, comprising the following steps:

[0008] (1) loading boron nitride powder on a conductive substrate to prepare a boron nitride electrode;

[0009] (2) Electrodepositing the boron nitride electrode in a copper-containing electrolyte to electroplate copper on the surface of the boron nitride to obtain a copper-based electrode.

[0010] As a preferred technical solution, the preparation method of the boron nitride powder is: boric acid and melamine are mixed and dispersed in water, then heated and stirred, the obtained white precipitate is dried and ground, and then calcined under an inert atmosphere to obtain boron nitride, the prepared boron nitride is ground into powder, ultrasonically dispersed after adding water, and the upper clear liquid is taken and dried.

[0011] As a preferred technical solution, in the step (1), boron nitride and carbon powder are dispersed in an aqueous solution containing nafion and isopropanol to prepare an ink which is then drop-coated on a conductive substrate to prepare a boron nitride electrode.

[0012] As a preferred technical solution, in step (1), the loading amount of boron nitride on the conductive substrate is 1 to 10 mg / cm 2 .

[0013] As a preferred technical solution, in step (2), a three-electrode system is used, the working electrode is a boron nitride electrode, the counter electrode is a platinum electrode, the reference electrode is a silver-silver chloride electrode, the electrolyte contains sulfate and Cu-EDTA, and the electrodeposition adopts cyclic voltammetry.

[0014] As a preferred technical solution, the potential window of the cyclic voltammetry is -0.2 to -1.0 V vs. Ag / AgCl, the number of scans is 100 to 400, and the scan rate is 10 to 100 mV / s.

[0015] As a preferred technical solution, the concentration range of Cu-EDTA in the electrolyte is 0.1 to 0.5 mmol / L.

[0016] As a preferred technical solution, the concentration range of Cu-EDTA in the electrolyte is 0.3 to 0.4 mmol / L.

[0017] The invention also provides a copper-based electrode prepared by the method.

[0018] The present invention also provides the use of the copper-based electrode in electrochemical reduction removal of florfenicol. The copper-based electrode is used as a working electrode and the applied voltage range is -1V to -1.3V vs. Ag / AgCl.

[0019] The beneficial effects of the present invention are:

[0020] 1. The present invention first loads boron nitride on a conductive substrate, and then electro-deposits copper on the surface of the boron nitride. Compared with electro-depositing copper directly on the conductive substrate, the boron nitride has a large specific surface area, which is conducive to uniform copper deposition, and boron nitride is conducive to breaking the complex, so that copper can be deposited better, solving the problem of poor effect of depositing complex copper by conventional electro-deposition methods.

[0021] 2. The Cu-EDTA (EDTA complexed copper, EDTA is ethylenediaminetetraacetic acid) used in the electrodeposition of the present invention realizes the resource utilization of copper-containing complex wastewater.

[0022] 3. The copper-based electrode prepared by the present invention can achieve a removal efficiency of 99.1% by electrochemically reducing the antibiotic florfenicol, greatly improving the biodegradability and oxidizability of florfenicol, which is conducive to further treatment by conventional municipal sewage treatment equipment, avoiding the generation of toxic by-products and reducing treatment energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to make the purpose, technical solution and beneficial effects of the present invention clearer, the present invention provides the following drawings for illustration:

[0024] Figure 1 This is the X-ray diffraction pattern of the boron nitride prepared in Example 1.

[0025] Figure 2 Transmission electron microscope image of the copper-based electrode prepared in Example 2 and energy spectrum analysis diagram of copper, boron and nitrogen elements.

[0026] Figure 3 The figure is a comparison of the electrochemical reduction effect of the CB electrode prepared in Example 1, the Cu / BN prepared in Example 2, the Cu / CB electrode prepared in Comparative Example 1, and the CB electrode for removing florfenicol.

[0027] Figure 4 This figure compares the electrochemical reduction removal of florfenicol by copper-based electrodes prepared with different concentrations of Cu-EDTA.

[0028] Figure 5 This is a diagram comparing the effect of electrochemical reduction of florfenicol removal by the copper-based electrode prepared in Example 2 at different voltages. DETAILED DESCRIPTION

[0029] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0030] Example 1

[0031] Boron nitride material is prepared by a combined method of self-assembly and high-temperature calcination, and a boron nitride electrode is prepared:

[0032] (1) Disperse 1.24 g of boric acid (H3BO3) and 1.26 g of melamine (C3N6H6) in 100 mL of deionized water;

[0033] (2) heating the mixture to 85° C. and maintaining it under stirring for 12 hours to allow the self-assembly process to proceed; after evaporating the solvent, the obtained white precipitate was further dried overnight;

[0034] (3) grinding the final precursor into powder, and annealing it at 1000°C for 3 h at a heating rate of 10°C / min under nitrogen protection to finally obtain boron nitride material, which was stored under anhydrous conditions;

[0035] (4) Grinding the prepared boron nitride material, dissolving it in water and then ultrasonically shaking it, taking the supernatant, drying it in an oven at 85° C. for 24 hours, and setting it aside for later use;

[0036] (5) Weigh 30 mg of boron nitride and 4 mg of carbon powder into a beaker, then add 1 mL of isopropanol and 4 mL of deionized water, and then add 50 μL of nafion solution; ultrasonically vibrate the above solution for 10 minutes to make it evenly dispersed, and then titrate the ultrasonicated solution to 6 cm 2 Boron nitride electrode (BN) was made on carbon paper.

[0037] Figure 1 This is the X-ray diffraction pattern of the boron nitride prepared in Example 1. The peaks in the figure are all X-ray diffraction peaks of boron nitride, and there are no other impurity peaks.

[0038] Example 2

[0039] The boron nitride electrode prepared in Example 1 was used as the electrode substrate, and a copper-based electrode (Cu / BN) was prepared by electrodeposition:

[0040] (1) A three-electrode system was used, with a boron nitride electrode as the working electrode, a platinum electrode as the counter electrode, and a silver-silver chloride electrode as the reference electrode. The electrolyte contained sodium sulfate (0.1 mol / L) and Cu-EDTA, and the concentration of Cu-EDTA was 0.3 mmol / L.

[0041] (2) The electrodeposition was carried out by cyclic voltammetry with a potential window range of -0.2 to -1.0 V vs. Ag / AgCl, a scan number of 200 cycles, and a scan rate of 100 mV / s.

[0042] Figure 2 The transmission electron microscope image of the copper-based electrode prepared in Example 2 and the energy spectrum elemental analysis image of copper, boron and nitrogen show that the morphology of the copper-based electrode is consistent with that of boron nitride, which is rod-shaped with a width of 0.3 μm, and copper atoms are evenly distributed on the surface of the rod-shaped boron nitride.

[0043] Comparative Example 1

[0044] Directly electrodeposit copper on carbon paper to prepare Cu / CB electrode:

[0045] (1) A three-electrode system was used, with carbon paper (CB) as the working electrode, platinum electrode as the counter electrode, silver-silver chloride electrode as the reference electrode, and the electrolyte containing sulfate and Cu-EDTA, with the concentration of Cu-EDTA being 0.3 mmol / L;

[0046] (2) The electrodeposition was carried out by cyclic voltammetry with a potential window range of -0.2 to -1.0 V vs. Ag / AgCl, a scan number of 200 cycles, and a scan rate of 100 mV / s.

[0047] Example 3

[0048] Comparison of the electrochemical reduction effects of the BN electrode prepared in Example 1, the Cu / BN electrode prepared in Example 2, the Cu / CB electrode prepared in Comparative Example 1 and the pure carbon paper electrode (CB) on the removal of florfenicol:

[0049] (1) A three-electrode system is used for electrochemical reduction reaction, wherein the working electrodes are BN electrode, Cu / BN electrode, Cu / CB electrode and CB electrode, the counter electrode is a platinum electrode, and the reference electrode is a silver-silver chloride electrode;

[0050] (2) adding 40 mL of 0.1 m / L saturated sodium sulfate solution into the dual-chamber reactor;

[0051] (3) After taking 0.16 mL of solution from the cathode chamber, add 0.16 mL of 5 g / L florfenicol solution;

[0052] (4) The applied voltage was -1.2 V vs. Ag / AgCl and the reaction time was 2.5 hours.

[0053] Figure 3The electrochemical reduction removal effect diagram of florfenicol by comparing the CB electrode of Example 1, the Cu / BN prepared in Example 2, the Cu / CB electrode prepared in Comparative Example 1, and the CB electrode shows that Cu / BN has the best removal effect on florfenicol in the electrochemical reduction reaction, reaching 99.1%.

[0054] Example 4

[0055] The boron nitride electrode prepared in the above Example 1 was used as the electrode substrate, and different copper-based electrodes were prepared by electrodeposition based on different Cu-EDTA concentrations:

[0056] (1) A three-electrode system was used, with a boron nitride electrode as the working electrode, a platinum electrode as the counter electrode, and a silver-silver chloride electrode as the reference electrode. The electrolyte contained sodium sulfate (0.1 mol / L) and Cu-EDTA, and the concentration of Cu-EDTA was set to 0.1 mmol / L, 0.2 mmol / L, 0.3 mmol / L, 0.4 mmol / L, and 0.5 mmol / L, respectively;

[0057] (2) The electrodeposition was carried out by cyclic voltammetry with a potential window range of -0.2 to -1.0 V vs. Ag / AgCl, a scan number of 200 cycles, and a scan rate of 100 mV / s.

[0058] The copper-based electrodes prepared with different Cu-EDTA concentrations were applied to the electrochemical reduction reaction for the removal of florfenicol:

[0059] (1) A three-electrode system was used for the electrochemical reduction reaction, wherein the working electrode was a copper-based electrode prepared with different Cu-EDTA concentrations, the counter electrode was a platinum electrode, and the reference electrode was a silver-silver chloride electrode;

[0060] (2) Add 40 mL of 0.1 m / L saturated sodium sulfate solution into each of the two-chamber reactors;

[0061] (3) After taking 0.16 mL of sodium sulfate solution from the cathode chamber, add 0.16 mL of 5 g / L florfenicol solution;

[0062] (4) The applied voltage was -1.2 V vs. Ag / AgCl and the reaction time was 2.5 hours.

[0063] Figure 4 This is a diagram comparing the electrochemical reduction removal of florfenicol by copper-based electrodes prepared with different concentrations of Cu-EDTA. The electrochemical reduction removal of florfenicol by copper-based electrodes prepared with Cu-EDTA concentrations of 0.3 and 0.4 mmol / L were better.

[0064] Example 5

[0065] Comparison of the effect of electrochemical reduction of Cu / BN prepared in Example 2 on removal of florfenicol at different voltages:

[0066] (1) A three-electrode system was used for the electrochemical reduction reaction, wherein the working electrode was a Cu / BN electrode, the counter electrode was a platinum electrode, and the reference electrode was a silver-silver chloride electrode.

[0067] (2) Add 40 mL of 0.1 m / L saturated sodium sulfate solution into each of the two-chamber reactors;

[0068] (3) After taking 0.16 mL of sodium sulfate solution from the cathode chamber, add 0.16 mL of 5 g / L florfenicol solution;

[0069] (4) The applied voltage range is -1 V to -1.3 V vs. Ag / AgCl, and the reaction time is 2.5 hours.

[0070] Figure 5 To compare the effect of electrochemical reduction of florfenicol removal by the copper-based electrode prepared in Example 2 at different voltages, the reaction effect at a voltage of -1.2 V vs. Ag / AgCl is the best.

[0071] The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or changes made by technicians in the technical field on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. Application of a copper-based electrode in electrochemical reduction removal of florfenicol, characterized in that: The method for preparing the copper-based electrode comprises the following steps: (1) loading boron nitride powder on a conductive substrate to prepare a boron nitride electrode; (2) subjecting the boron nitride electrode to an electroplating reaction in a copper-containing electrolyte to electroplating copper on the surface of the boron nitride to obtain a copper-based electrode; The copper-based electrode was used as a working electrode, and the applied voltage range was -1V to -1.3V vs. Ag / AgCl.

2. The use of the copper-based electrode according to claim 1 in electrochemical reduction removal of florfenicol, characterized in that: The preparation method of the boron nitride powder is as follows: boric acid and melamine are mixed and dispersed in water, then heated and stirred, the obtained white precipitate is dried and ground, and then calcined under an inert atmosphere to obtain boron nitride, the prepared boron nitride is ground into powder, water is added and ultrasonically dispersed, and the upper clear liquid is taken and dried.

3. The use of the copper-based electrode according to claim 1 in electrochemical reduction removal of florfenicol, characterized in that: In the step (1), boron nitride and carbon powder are dispersed in an aqueous solution containing nafion and isopropanol to prepare ink, which is then drop-coated on a conductive substrate to prepare a boron nitride electrode.

4. The use of the copper-based electrode according to claim 3 in electrochemical reduction removal of florfenicol, characterized in that: In the step (1), the loading amount of boron nitride on the conductive substrate is 1 to 10 mg / cm 2 .

5. The use of the copper-based electrode according to claim 1 in electrochemical reduction removal of florfenicol, characterized in that: In the step (2), a three-electrode system is used, wherein the working electrode is a boron nitride electrode, the counter electrode is a platinum electrode, the reference electrode is a silver-silver chloride electrode, the electrolyte contains sulfate and Cu-EDTA, and the electrodeposition is carried out by cyclic voltammetry.

6. Use of the copper-based electrode according to claim 5 in electrochemical reduction removal of florfenicol, characterized in that: The potential window of the cyclic voltammetry method is -0.2 to -1.0 V vs. Ag / AgCl, the number of scans is 100 to 400, and the scan rate is 10 to 100 mV / s.

7. Use of the copper-based electrode according to claim 5 in electrochemical reduction removal of florfenicol, characterized in that: The concentration range of Cu-EDTA in the electrolyte is 0.1-0.5 mmol / L.

8. Use of the copper-based electrode according to claim 7 in electrochemical reduction removal of florfenicol, characterized in that: The concentration range of Cu-EDTA in the electrolyte is 0.3-0.4 mmol / L.

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