Method for preparing copper-tin composite electrode material based on scrap white copper and application thereof

Abstract

The application discloses a preparation method of copper-tin composite electrode material based on waste white copper and application thereof, belongs to the field of waste white copper recovery copper-based composite material preparation and glucose electrochemical detection, and is characterized in that waste white copper sulfuric acid solution is used as a copper metal precursor, silver wire is used as a cathode, waste white copper sulfuric acid solution added with tin oxide powder is used as an electrolyte, a waste white copper sheet is used as an anode, a copper-coated tin oxide composite material is synthesized on the silver wire through an electrochemical composite electrodeposition process, the copper-coated tin oxide composite material is subjected to low-temperature calcination in an argon-hydrogen mixed gas, and the copper-tin composite electrode material is obtained. The copper-tin composite electrode material prepared by the method has good electrochemical performance, and the preparation process is simple, so that the application of the copper-tin-based composite material in the field of electrochemical glucose sensors can be promoted.

Description

Technical Field

[0001] This invention belongs to the field of preparation of copper-based composite materials from recycled waste white copper and electrochemical detection of glucose, specifically relating to a method for preparing a copper-tin composite electrode material based on waste white copper and its application in glucose detection. Background Technology

[0002] Diabetes is one of the leading causes of death worldwide each year, and it also leads to several other complications such as kidney failure, stroke, and blindness. The number of people with diabetes has been increasing in recent years. The primary cause is insufficient insulin secretion from the pancreas, leading to elevated blood sugar, but it is also influenced by factors such as genetics, lifestyle, and viruses. Maintaining normal blood sugar levels is a key strategy for preventing diabetes-related complications; therefore, developing low-cost, simple, and rapid glucose detection methods is particularly important. Electrochemical glucose sensors have attracted much attention due to their high sensitivity, low detection limit, rapid response, and ease of operation. However, traditional electrochemical enzyme sensors are limited in practical applications due to their complex preparation methods, high cost, and susceptibility to inactivation caused by environmental factors such as temperature and pH. Transition metal-based non-enzymatic glucose sensors have attracted widespread attention from researchers due to their low cost, good stability, and excellent catalytic activity.

[0003] Studies have found that copper not only exhibits excellent conductivity in the electrocatalytic oxidation and detection of glucose, but also serves as a good active site center. On the other hand, cupronickel is a nickel-copper alloy with copper as the base metal and nickel as the main alloying element, possessing a silvery-white metallic luster. Because copper and nickel have similar atomic radii, they are infinitely miscible, and their corrosion resistance, heat resistance, and cold resistance are also excellent. To improve the alloy's microstructure and properties, appropriate amounts of zinc, iron, or manganese are often added to obtain zinc-copper, iron-copper, and manganese-copper alloys, which have wider applications. In recent years, with rapid economic growth and industrialization, the demand and consumption of cupronickel alloys have been continuously increasing, generating a large amount of waste cupronickel alloys. Due to the depletion of natural copper-nickel ore resources and environmental protection requirements, waste cupronickel alloys have gradually become an important copper metal resource. For large pieces of waste cupronickel alloy, due to the difficulty in crushing and the challenge in achieving metal separation through pyrometallurgy, traditional hydrometallurgical processes such as leaching, extraction, and electrowinning are mostly used for recycling. Although electrodeposition technology has advantages such as high dissolution efficiency, good working conditions, and high resource utilization, its industrial applications still face challenges such as complex processes, large reagent consumption, and secondary environmental pollution. Therefore, finding a simple recycling process for waste cupronickel is particularly important.

[0004] Compared to monometallic materials, bimetallic materials often exhibit better electron transfer rates and superior electrocatalytic activity due to the synergistic effect between the two elements. Based on this, this invention selected copper and tin and constructed copper-tin-based bimetallic catalysts using different methods for non-enzymatic electrochemical glucose detection. Summary of the Invention

[0005] The main objective of this invention is to provide a simple method for preparing a copper-tin composite electrode material with excellent glucose detection performance using waste white copper as a copper metal precursor. Specifically, a waste white copper sulfuric acid solution is used as the copper metal precursor, a silver wire as the cathode, and a waste white copper sulfuric acid solution with added tin oxide powder as the electrolyte. A simple electrochemical composite electrodeposition process is used to rapidly synthesize a copper-coated tin oxide composite material on the silver wire. The copper-coated tin oxide composite material is then calcined at low temperature in an argon-hydrogen mixed gas to obtain a copper-tin composite electrode material rich in vacancies and defects.

[0006] This invention provides a method for preparing a copper-tin composite electrode material based on waste white copper, comprising the following steps:

[0007] 1) Calcination of waste white copper yields waste white copper sheets with surface oxidation;

[0008] 2) The waste white copper sheet obtained in step 1) is immersed in sulfuric acid solution and heated to dissolve it, thus obtaining a sulfuric acid solution of waste white copper;

[0009] 3) The sulfuric acid solution of the waste white copper obtained in step 2) is used as a copper metal precursor. After adding tin dioxide powder, it is used as an electrolyte to dissolve the remaining waste white copper sheet or the calcined waste white copper sheet as the anode and the silver wire as the cathode. The electrolytic reaction is carried out. After cleaning and drying the cathode after electrolysis, a copper-coated tin oxide composite material is obtained, which is the precursor of the copper-tin composite electrode material.

[0010] 4) The precursor material obtained in step 3) is calcined in an argon-hydrogen mixed atmosphere in a tube furnace to obtain a copper-tin composite electrode material based on waste white copper.

[0011] The scrap nickel-nickel copper described in this invention is B17 type scrap nickel-nickel copper, which mainly contains three metallic elements: copper, zinc, and nickel, with copper content of 82%, zinc content of 15%, and nickel content of 3%.

[0012] The calcination process described in step 1) of this invention is carried out in a muffle furnace at a calcination temperature of 500℃~800℃ and a calcination time of 60min~180min.

[0013] The sulfuric acid solution concentration described in this invention is 0.01 mol / L to 5 mol / L.

[0014] The soaking temperature in step 2) of this invention is 25℃~95℃, and the reaction time is 50min~130min.

[0015] The concentration of the sulfuric acid solution for the waste white copper described in this invention is 0.005 mol / L to 3 mol / L.

[0016] The amount of tin dioxide powder added in this invention is 4 mg / L to 15 mg / L.

[0017] The electrolysis method described in this invention uses a voltage of -3 to -1.1V and a cathode current density of 0.01A / cm². 2 ~0.111A / cm 2 The electrolysis temperature is 25℃~55℃, the electrolysis time is 20min~60min, and the stirring speed is 200r / min~500r / min.

[0018] The chemical reactions that occur during the electrolysis process described in this invention are as follows:

[0019] Anode reaction: M → xe + M xe Cathode reaction: Cu 2+ +2e→Cu.

[0020] The precursor of the copper-tin composite electrode material of the present invention is Cu@SnO2. During the copper deposition process, tin dioxide nanoparticles are coated and deposited onto the electrode surface.

[0021] The present invention describes calcination in an argon-hydrogen mixed atmosphere, wherein the molar fraction of hydrogen in the mixed gas is 2-10%, the calcination temperature is 300℃-600℃, and the calcination time is 1h-3h.

[0022] The second aspect of the present invention provides a copper-tin composite electrode material based on waste white copper, which is prepared according to the method described in the first aspect.

[0023] The third aspect of this invention provides the application of a copper-tin composite electrode material based on waste white copper in a glucose sensor.

[0024] The copper-tin composite electrode material exhibits excellent stability, selectivity, and good analytical and detection performance.

[0025] The excellent analytical and detection performance stems from the rich interfacial structure and the synergistic catalytic effect of the bimetallic copper-tin.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. This invention employs a simple composite electrodeposition-low-temperature calcination process, using an acidic solution of waste white copper with added tin dioxide powder as the electrodeposition solution, to prepare a copper-tin composite electrode material with excellent detection performance. This method not only helps broaden research ideas on the resource utilization of waste white copper but also yields novel glucose sensor materials and reduces costs, thus possessing high economic value.

[0028] 2. This invention utilizes a simple composite electrodeposition-low-temperature calcination process to prepare transition metal-based composite electrode materials, achieving efficient glucose detection. This not only realizes one-step production from secondary resources to glucose sensors but also effectively avoids the problems of difficult multi-metal separation and high separation costs associated with waste white copper during processing.

[0029] 3. Compared with existing sensor fabrication processes, this method has a shorter process flow from secondary resources to composite electrode materials, simpler process, lower process cost, less demanding equipment requirements, and is easy to achieve large-scale production.

[0030] 4. The copper-tin composite electrode material prepared by the method of this invention exhibits good stability, selectivity, and analytical detection performance. This invention opens up a new avenue for efficient and low-cost non-enzymatic glucose detection, and also provides a novel research approach for the comprehensive and efficient recycling and utilization of waste white copper. Attached Figure Description

[0031] Figure 1 Morphological results of copper-tin composite electrode material;

[0032] Figure 2 Copper element distribution diagram on the surface of copper-tin composite electrode material;

[0033] Figure 3 Tin element distribution diagram on the surface of copper-tin composite electrode material;

[0034] Figure 4 Oxygen distribution on the surface of copper-tin composite electrode material;

[0035] Figure 5 Electrochemical impedance spectroscopy of copper-tin composite electrode material;

[0036] Figure 6 Multivariable wave cyclic curves of copper-tin composite electrode materials. Detailed Implementation

[0037] This invention discloses a method for preparing a copper-tin composite electrode material based on waste white copper. The waste white copper used is B17 type waste nickel white copper, which mainly contains three metal elements: copper, zinc, and nickel. The copper content is 82%, the zinc content is 15%, and the nickel content is 3%. The obtained copper-tin composite electrode material is applied to a non-enzymatic glucose electrochemical sensor.

[0038] A method for preparing a copper-tin composite electrode material based on waste white copper, the specific steps of which are as follows:

[0039] 1) Calcination of waste white copper yields waste white copper sheets with surface oxidation; the calcination process is carried out in a muffle furnace at a temperature of 500℃~800℃ for 60min~180min.

[0040] 2) The waste white copper sheet obtained in step 1) is immersed in a sulfuric acid solution with a concentration of 0.01mol / L to 5mol / L and heated to dissolve. The immersion temperature is 25℃ to 95℃ and the reaction time is 50min to 130min to obtain a sulfuric acid solution of waste white copper.

[0041] 3) Take the sulfuric acid solution (0.005 mol / L to 3 mol / L) of the waste white copper from step 2) as the copper metal precursor, and use it as the electrolyte after adding tin dioxide powder (4 mg / L to 15 mg / L). Dissolve the remaining waste white copper sheets or the oxidized waste white copper sheets as the anode, and use silver wire as the cathode for electrolysis. The electrolysis voltage is -3V to -1.1V, and the cathode current density is 0.01 A / cm². 2 ~0.111A / cm 2 The electrolysis temperature is 25℃~55℃, the electrolysis time is 20min~60min, and the stirring speed is 200r / min~500r / min. After cleaning and drying the cathode after electrolysis, a copper-coated tin oxide composite material is obtained, which is the precursor of copper-tin composite electrode material.

[0042] 4) The precursor material obtained in step 3) is calcined in an argon-hydrogen mixed atmosphere in a tube furnace to obtain a copper-tin composite electrode material based on waste white copper. The molar fraction of hydrogen in the mixed gas is 2% to 10%, the calcination temperature is 300℃ to 600℃, and the calcination time is 1 to 3 hours.

[0043] Example 1

[0044] Using surface-oxidized waste white copper sheets as the anode, 200 mL of a 0.5 mol / L sulfuric acid solution containing 12 mg of tin dioxide powder was used as the electrolyte. A clean silver wire was used as the cathode. Electrolysis was carried out in a water bath at 200 rpm for 20 min with stirring, at a temperature of 30 °C. Electrode material was then deposited by constant current electrolysis at a deposition current of 0.01 A / cm. 2After cleaning and drying the cathode after electrolysis, a precursor for copper-tin composite electrode material is obtained. The precursor material is then calcined in an argon-hydrogen mixed atmosphere in a tube furnace, wherein the molar fraction of hydrogen in the mixed gas is 8%, the calcination temperature is 300℃, and the calcination time is 1 hour, to obtain a copper-tin composite electrode material based on waste white copper.

[0045] The morphology of the copper-tin composite electrode material prepared in Example 1 is as follows: Figure 1 As shown, the distributions of copper, tin, and oxygen elements on the surface are as follows: Figure 2 , 3 As shown in Figure 4, the electrochemical impedance spectroscopy of this copper-tin composite electrode material is as follows: Figure 5 As shown, the multi-fold wave cyclic curve is as follows: Figure 6 As shown.

[0046] Example 2

[0047] The remaining waste white copper sheet dissolved in sulfuric acid solution was used as the anode. 200 mL of a sulfuric acid solution containing 0.1 mol / L waste white copper with added 8 mg of tin dioxide powder was used as the electrolyte. A clean silver wire was used as the cathode. Electrolysis was carried out in a water bath at 300 rpm for 35 min with stirring, and the electrolysis temperature was 55℃. Electrode material was prepared by constant voltage electrolytic deposition at a deposition voltage of -2V. After cleaning and drying the cathode after electrolysis, a precursor for the copper-tin composite electrode material was obtained. The precursor material was calcined in a tube furnace under an argon-hydrogen mixed atmosphere, where the molar fraction of hydrogen in the mixed gas was 6%, at 300℃ for 2 hours, to obtain the copper-tin composite electrode material based on waste white copper.

[0048] Example 3

[0049] Using surface-oxidized waste white copper sheets as the anode, 200 mL of a 1 mol / L sulfuric acid solution containing 10 mg of tin dioxide powder was used as the electrolyte. A clean silver wire was used as the cathode. Electrolysis was carried out in a water bath at 500 rpm for 60 min with stirring, at a temperature of 35 °C. Electrode material was then deposited by constant current electrolysis at a deposition current of 0.05 A / cm. 2 After cleaning and drying the cathode following electrolysis, a precursor for copper-tin composite electrode material is obtained. The precursor material is then calcined in a tube furnace under an argon-hydrogen mixed atmosphere, wherein the molar fraction of hydrogen in the mixed gas is 2%, the calcination temperature is 500℃, and the calcination time is 2 hours, to obtain a copper-tin composite electrode material based on waste white copper.

[0050] Example 4

[0051] The remaining waste white copper sheet dissolved in sulfuric acid solution was used as the anode. 200 mL of a 3 mol / L sulfuric acid solution containing 16 mg of tin dioxide powder was used as the electrolyte. A clean silver wire was used as the cathode. Electrolysis was carried out in a water bath at 500 rpm for 60 min with stirring, at a temperature of 40 °C. Electrode material was deposited by constant voltage electrolysis at a deposition voltage of -1 V. After cleaning and drying the cathode after electrolysis, a precursor for the copper-tin composite electrode material was obtained. The precursor material was calcined in a tube furnace under an argon-hydrogen mixed atmosphere, where the molar fraction of hydrogen in the mixed gas was 2%, at 600 °C for 1 hour, yielding the copper-tin composite electrode material based on waste white copper.

[0052] The present invention has been described through the above embodiments. However, it should be understood that the above embodiments are for illustrative purposes only and are not intended to limit the present invention to the scope of the described embodiments. Furthermore, those skilled in the art will understand that the present invention is not limited to the above embodiments, and many more variations and modifications can be made based on the teachings of the present invention, all of which fall within the scope of protection claimed by the present invention.

Claims

1. A method for producing a copper-tin composite electrode material based on spent white copper, characterized in that, The copper-coated tin oxide composite material is obtained by synthesizing the copper-coated tin oxide composite material on the silver wire through the electrochemical composite electrodeposition process, and then performing low-temperature calcination on the copper-coated tin oxide composite material in an argon-hydrogen mixed gas.

2. The method of claim 1, wherein the copper-tin composite electrode material based on scrap cupronickel is prepared by the steps of: The method comprises the following steps: ​ 1) performing calcination treatment on the waste white copper to obtain waste white copper sheet with an oxidized surface; 2) performing heating dissolution on the waste white copper sheet obtained in step 1) in a sulfuric acid solution to obtain a waste white copper sulfuric acid dissolution solution; 3) performing electrolysis reaction by taking the waste white copper sulfuric acid dissolution solution obtained in step 2) as a copper metal precursor, adding tin dioxide powder as an electrolyte, and dissolving the remaining waste white copper sheet or the waste white copper sheet after calcination treatment as an anode, and taking silver wire as a cathode, and then performing cleaning and drying on the cathode after electrolysis to obtain the copper-coated tin oxide composite material, i.e., a precursor of the copper-tin composite electrode material; 4) performing calcination on the precursor material obtained in step 3) in a tube furnace in an argon-hydrogen mixed atmosphere to obtain the copper-tin composite electrode material based on waste white copper.

3. A method of producing a copper-tin composite electrode material based on scrap cupro-nickel according to claim 2, characterized in that, The waste white copper is B17 type waste nickel white copper, mainly containing three metal elements of copper, zinc and nickel, wherein the content of copper is 82%, the content of zinc is 15%, and the content of nickel is 3%.

4. The method for preparing a copper-tin composite electrode material based on waste white copper according to claim 2, characterized in that, The calcination process in step 1) is performed in a muffle furnace, the calcination temperature is 500-800 DEG C, and the calcination time is 60-180 min.

5. The method for preparing a copper-tin composite electrode material based on waste white copper according to claim 2, characterized in that, The concentration of the sulfuric acid solution in step 2) is 0.01-5 mol / L, the soaking temperature is 25-95 DEG C, and the reaction time is 50-130 min.

6. The method of claim 2, wherein the copper-tin composite electrode material based on scrap cupronickel is prepared by the steps of: The concentration of the waste white copper sulfuric acid dissolution solution in step 3) is 0.005-3 mol / L, and the addition amount of the tin dioxide powder is 4-15 mg / L. ​ 7. The method for preparing a copper-tin composite electrode material based on waste white copper according to claim 2, characterized in that, The electrolysis voltage in step 3) is -3V to -1.1V, and the cathode current density is 0.01A / cm 2 ~0.111A / cm 2 The temperature during electrolysis is 25°C to 55°C, the electrolysis time is 20min to 60min, and the stirring speed is 200r / min to 500r / min.

8. The method for preparing a copper-tin composite electrode material based on waste white copper according to claim 2, characterized in that, The precursor of the copper-tin composite electrode material is Cu@SnO2, and the tin dioxide nanoparticles are coated and deposited on the electrode surface during the copper deposition process.

9. The method for preparing a copper-tin composite electrode material based on waste white copper according to claim 2, characterized in that, The calcination in step 4) is performed in an argon-hydrogen mixed atmosphere, wherein the molar fraction of hydrogen in the mixed gas is 2-10%, the calcination temperature is 300-600 DEG C, and the calcination time is 1-3 h.

10. Application of the copper-tin composite electrode material based on waste white copper prepared by the preparation method in any one of claims 1-9 in a glucose sensor.

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