An electrochemical preparation method for staggered cuprous oxide micron cubes

Abstract

This invention discloses an electrochemical method for preparing staggered cuprous oxide micron-sized cubes, belonging to the field of electrode material preparation technology. The method utilizes a redox reaction at room temperature as the main synthesis mechanism, using clean copper foam as the copper source. The reaction is carried out in a mixed solution of alkaline solution and persulfate for a certain time. The copper foam intermediate is then sequentially cleaned, vacuum dried, and calcined. Subsequently, in a three-electrode system, the treated copper foam is used as the working electrode and electrochemically treated in a selenite solution to prepare a highly crystalline cuprous oxide material exhibiting a staggered micron-sized cube morphology with a smooth and flat cube surface. When applied to the energy storage field, it achieves a high areal specific capacity even at high current densities, with a maximum areal specific capacity of 1556 mF / cm². 2 This invention is simple to operate, has a short preparation cycle, is energy-saving, efficient, and inexpensive.

Description

Technical Field

[0001] This invention belongs to the field of electrode material preparation technology, and specifically relates to an electrochemical preparation method of staggered cuprous oxide micron cubes. Background Technology

[0002] Cuprous oxide is an important copper compound with unique physical and chemical properties, finding wide applications in various fields. There are multiple technical routes for preparing cuprous oxide, such as chemical precipitation, solvothermal methods, and reduction methods. The morphology of cuprous oxide can be controlled through specific preparation methods. For example, hydrothermal synthesis can produce cuprous oxide with different morphologies, such as nanoparticles, nanowires, and nanosheets. Precipitation methods typically yield cuprous oxide in a particulate form, while the sol-gel method can potentially produce cuprous oxide with a porous structure. Furthermore, the crystal morphology of cuprous oxide can also be spherical, octahedral, cubic, etc., and the formation of these morphologies is also influenced by the preparation method and conditions. In practical applications, appropriate preparation methods can be selected to obtain cuprous oxide with specific morphologies as needed.

[0003] Current literature primarily reports on nano-cuprous oxide, with diverse synthesis methods. However, research on the preparation of micron-sized cuprous oxide is relatively limited. One study used copper sulfate pentahydrate as the copper source and D-sorbitol as the reducing agent to prepare cuprous oxide microrods via a hydrothermal method (Functional Materials, 2007, 38, 2255-2256). Another study used copper chloride as the copper source, sodium acetate as the precipitant, polyethylene glycol as the morphology control agent, and glucose as the reducing agent to prepare micron-sized cuprous oxide cubes via a hydrothermal method in a mixed solvent of water and ethylene glycol (Chemical Research and Application, 2013, 25, 525-528). Micron-sized cuprous oxide has broad application prospects in photocatalysis and photothermal fields, and its unique morphology enables it to exhibit excellent performance in these areas. Therefore, the controllable preparation of micron-sized cuprous oxide is of great significance. Summary of the Invention

[0004] Given the limitations of existing methods for preparing micron-sized cuprous oxide and the resulting lack of variety in product morphology, the present invention aims to provide an electrochemical preparation method for staggered cuprous oxide micron-sized cubes. This method has the advantages of simple preparation process, easy operation, short preparation cycle, energy saving, high efficiency, and low cost. At the same time, the obtained staggered cuprous oxide micron-sized cube material has a high areal specific capacitance when used as a supercapacitor electrode material.

[0005] To achieve the above-mentioned technical objectives, this invention, through extensive experimental research and unremitting efforts, ultimately adopted a redox reaction at room temperature as the main synthesis mechanism. Clean copper foam was used as the copper source, and the reaction was carried out in a mixed solution of alkaline solution and persulfate for a certain period of time. The copper foam intermediate was then sequentially cleaned, vacuum dried, and calcined. Subsequently, in a three-electrode system, the processed copper foam was used as the working electrode, and it was electrochemically treated in a selenite solution to prepare a highly crystalline cuprous oxide material. This material exhibits an interlaced micron-sized cubic morphology with a smooth and flat cubic surface.

[0006] Specifically, the objective of this invention is achieved according to the following technical solution: an electrochemical preparation method for staggered cuprous oxide micron-sized cubes, the method comprising the following steps:

[0007] Step 1: Clean the cut foamed copper in acetone, hydrochloric acid and deionized water by ultrasonic cleaning in sequence. After wiping it dry, vacuum dry it at 50-60℃ for 3-6 hours.

[0008] Step 2: Place the copper foam obtained in Step 1 in a mixed solution of alkaline solution and persulfate solution, wherein the molar ratio of hydroxide ions in the alkaline solution to persulfate ions in the persulfate solution is (100-200):1. React at room temperature for 12-36 minutes, turning the copper foam over every 5-7 minutes. After the reaction is complete, wash the copper foam intermediate with deionized water and then vacuum dry it at 50-60°C for 3-6 hours.

[0009] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 2-10℃ / min to 190-230℃ for 1.5-3.5h.

[0010] Step 4: Using a 14.4–54.1 mmol / L selenite solution as the electrolyte, the copper foam obtained in Step 3 was electrochemically treated in a three-electrode system. Following washing with deionized water, it was vacuum dried at 50–60 °C for 3–6 h to prepare interlaced cuprous oxide microcubic material supported on a copper foam substrate. The resulting material exhibits an interlaced microcubic morphology with smooth and flat cubic surfaces.

[0011] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes as described above, the specific operation of the drying process in step 1 is as follows: the cleaned copper foam is arranged in sequence in a petri dish, and the enriched moisture on its surface is absorbed with lens paper.

[0012] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes as described above, the alkaline solution in step 2 is an aqueous solution of sodium hydroxide and / or potassium hydroxide.

[0013] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes as described above, the persulfate in step 2 is one or a mixture of two or more of sodium persulfate, potassium persulfate, and ammonium persulfate.

[0014] More preferably, in the electrochemical preparation method of the interleaved cuprous oxide micron cubes as described above, step 3 involves heating the material in a muffle furnace to 200–210°C at a heating rate of 5–10°C / min and calcining it for 2.5–3.5 h.

[0015] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes as described above, the preparation method of the selenite solution in step 4 is as follows: selenium dioxide is added to deionized water, the mass ratio of selenium dioxide to deionized water is (0.0016~0.006):1, and the mixture is stirred at room temperature for 20~35 min.

[0016] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes as described above, the three-electrode system in step 4 is as follows: the working electrode is the copper foam obtained in step 3, the counter electrode is a platinum sheet electrode, the reference electrode is an Ag / AgCl electrode, and the electrolyte is a selenite solution.

[0017] More preferably, in the electrochemical preparation method of the interleaved cuprous oxide micron cubes described above, the three-electrode system in step 4 is as follows: the working electrode is the copper foam obtained in step 3, and the counter electrode is a 1.0*1.0cm... 2 The electrode is a platinum sheet electrode, the reference electrode is an Ag / AgCl electrode, and the electrolyte is a 50 mL selenite solution.

[0018] More preferably, in the electrochemical preparation method of the staggered cuprous oxide micron cubes described above, the parameters of the electrochemical treatment in step 4 are as follows: cyclic voltammetry scanning is performed in a low voltage range of -1.3 to -1.0 V and a high voltage range of 0 to 0.3 V, with a scan rate of 3 to 10 mV s. -1 The number of scans is 2 to 6.

[0019] Furthermore, the present invention also provides the above-mentioned interlaced cuprous oxide microcube material prepared by an electrochemical preparation method and its application, wherein the above-mentioned interlaced cuprous oxide microcube is used in a supercapacitor.

[0020] Compared with existing technologies, the staggered cuprous oxide microcubic material prepared by this invention has the following advantages and advancements:

[0021] (1) In this invention, copper foam is used as the copper source. The staggered cuprous oxide micron cubes are grown in situ on the copper foam and can be directly used as an integrated electrode for supercapacitors.

[0022] (2) The micron-sized cuprous oxide synthesized in this invention has the characteristics of chemical stability and is not easily altered. This allows the material to maintain its original properties under a wide range of application conditions.

[0023] (3) The micron-sized cuprous oxide synthesized in this invention has a unique morphology, consisting of interlocking cubic structures. This novel morphology gives it unique physicochemical properties and application prospects, and it has great potential and value in multiple fields.

[0024] (4) The selenite acid used in this invention has a certain reducing property. When combined with the electrochemical cyclic voltammetric dissolution and deposition method, it has dual synthesis advantages, which can realize the reduction of copper oxide to cuprous oxide and the precise control of the dissolution and deposition process of cuprous oxide.

[0025] (5) Compared with other synthesis methods, the electrochemical method used in this invention has the advantages of simple preparation process, easy operation and low synthesis temperature, as well as the advantage of precise control of its structure by adjusting electrochemical parameters.

[0026] (6) When the material prepared in this invention is used directly as an integral electrode as the positive electrode material of a supercapacitor, it can exhibit excellent areal specific capacitance, which can provide innovative technical support for the development of high-performance supercapacitors and has important research significance and application value. Attached Figure Description

[0027] Figure 1 This is an XRD pattern of an interleaved cuprous oxide microcubic material prepared in Example 1 of this invention;

[0028] Figure 2 This is one of the SEM images of an interleaved cuprous oxide microcubic material prepared in Example 1 of this invention;

[0029] Figure 3 This is the second SEM image of an interleaved cuprous oxide microcubic material prepared in Example 1 of this invention;

[0030] Figure 4 This is the third SEM image of an interleaved cuprous oxide microcubic material prepared in Example 1 of this invention;

[0031] Figure 5 This is the CV curve of an interleaved cuprous oxide micron-cubic material prepared in Example 1 of this invention at different scanning speeds;

[0032] Figure 6 The GCD curves of an interleaved cuprous oxide micron-cubic material prepared in Example 1 of this invention are shown at different current densities.

[0033] Figure 7This invention relates to an example of an interleaved cuprous oxide micron-cubic material prepared in Example 1 of this invention, at a current density of 30 mA / cm². -2 Cyclic stability test curves at various times.

[0034] Figure 8 This is a SEM image of an interleaved cuprous oxide micron-cubic material prepared in Example 2 of this invention;

[0035] Figure 9 This is a SEM image of an interleaved cuprous oxide micron-cubic material prepared in Example 3 of this invention;

[0036] Figure 10 This is a SEM image of an interleaved cuprous oxide microcubic material prepared in Example 4 of this invention;

[0037] Figure 11 This is a SEM image of an interleaved cuprous oxide microcubic material prepared in Example 5 of this invention;

[0038] Figure 12 This is a SEM image of an interleaved cuprous oxide micron-cubic material prepared in Example 6 of this invention. Detailed Implementation

[0039] The preparation method of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0040] Example 1:

[0041] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0042] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0043] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of potassium hydroxide and potassium persulfate in 20 mL. The concentration of potassium hydroxide in the mixed solution is 1.2 mol / L and the concentration of potassium persulfate is 0.012 mol / L. React at room temperature for 18 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0044] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, heat it to 210°C in a muffle furnace at a heating rate of 5°C / min, and calcine for 2.5 hours.

[0045] Step 4: Add 100 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.1V and a high voltage range of 0.1V, at a scan rate of 5mV / s. -1 The scanning circle number was 2 circles. After washing with deionized water, it was vacuum dried at 60℃ for 6 hours to prepare interlaced cuprous oxide micron-cubic material loaded on a copper foam substrate.

[0046] Example 2:

[0047] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0048] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0049] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of sodium hydroxide and sodium persulfate in 20 mL. The concentration of sodium hydroxide in the mixed solution is 1.2 mol / L and the concentration of sodium persulfate is 0.012 mol / L. React at room temperature for 18 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0050] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 5℃ / min to 200℃ for 3.5h.

[0051] Step 4: Add 100 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.2V and a high voltage range of 0.2V, at a scan rate of 5 mV / s. -1 The scanning circle number was 3 revolutions. The material was then washed with deionized water and vacuum dried at 60℃ for 6 hours to prepare interleaved cuprous oxide micron-cubic material supported on a copper foam substrate.

[0052] Example 3:

[0053] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0054] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0055] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of potassium hydroxide and potassium persulfate in 20 mL. The concentration of potassium hydroxide in the mixed solution is 1.2 mol / L and the concentration of potassium persulfate is 0.008 mol / L. React at room temperature for 24 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0056] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 10℃ / min to 220℃ for 2.0h.

[0057] Step 4: Add 100 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.2V and a high voltage range of 0.2V at a scan rate of 10 mV / s. -1 The scanning circle number was 6 revolutions. The material was then washed with deionized water and vacuum dried at 60℃ for 6 hours to prepare interleaved cuprous oxide micron-cubic material supported on a copper foam substrate.

[0058] Example 4:

[0059] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0060] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0061] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of potassium hydroxide and ammonium persulfate in 20 mL. The concentration of potassium hydroxide in the mixed solution is 1.2 mol / L and the concentration of ammonium persulfate is 0.006 mol / L. React at room temperature for 30 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0062] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 5℃ / min to 190℃ for 3.5h.

[0063] Step 4: Add 300 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.1V and a high voltage range of 0.1V, at a scan rate of 3mV / s. -1 The scanning circle number was 2 circles. After washing with deionized water, it was vacuum dried at 60℃ for 6 hours to prepare interlaced cuprous oxide micron-cubic material loaded on a copper foam substrate.

[0064] Example 5:

[0065] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0066] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0067] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of potassium hydroxide and potassium persulfate in 20 mL. The concentration of potassium hydroxide in the mixed solution is 1.2 mol / L and the concentration of potassium persulfate is 0.006 mol / L. React at room temperature for 30 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0068] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 5℃ / min to 230℃ for 1.5h.

[0069] Step 4: Add 80 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.2V and a high voltage range of 0.2V, at a scan rate of 5 mV / s. -1 The scanning circle number was 3 revolutions. The material was then washed with deionized water and vacuum dried at 60℃ for 6 hours to prepare interleaved cuprous oxide micron-cubic material supported on a copper foam substrate.

[0070] Example 6:

[0071] An electrochemical method for preparing staggered cuprous oxide micron-sized cubes, specifically comprising the following steps:

[0072] Step 1: Clean the cut copper foam (1.0cm*1.0cm) sequentially with acetone, 1.0mol / L hydrochloric acid solution and deionized water by ultrasonic cleaning. Arrange the cleaned copper foam in petri dishes, absorb the accumulated moisture on the surface with lens paper, and vacuum dry at 60℃ for 6h.

[0073] Step 2: Take one piece of copper foam obtained in Step 1 and place it in a mixed solution of sodium hydroxide and potassium persulfate in 20 mL. The concentration of sodium hydroxide in the mixed solution is 1.2 mol / L and the concentration of potassium persulfate is 0.008 mol / L. React at room temperature for 12 min, turning it over every 6 min. Wash the copper foam intermediate with deionized water and dry it under vacuum at 60 °C for 6 h.

[0074] Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, heat it to 200°C in a muffle furnace at a heating rate of 2°C / min, and calcine for 3.5 hours.

[0075] Step 4: Add 80 mg of selenium dioxide to 50 mL of deionized water and stir at room temperature for 30 min to obtain a selenite solution, which will be used as the electrolyte. In the three-electrode system, the copper foam obtained in Step 3 will be used as the working electrode, with a diameter of 1.0 x 1.0 cm. 2 A platinum sheet electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. Cyclic voltammetry scans were performed in a low voltage range of -1.3V and a high voltage range of 0.0V, at a scan rate of 5mV / s. -1 The scanning circle was 3 revolutions. The material was then washed with deionized water and vacuum dried at 60℃ for 6 hours to prepare interleaved cuprous oxide microcubic material supported on a copper foam substrate.

[0076] like Figure 1The image shown is an XRD pattern of an interleaved cuprous oxide micron-sized cubic material prepared in Example 1 of this invention. It can be seen that the material synthesized in this invention is cuprous oxide and has high crystallinity. The copper diffraction peaks originate from the copper foam substrate.

[0077] like Figure 2 The image shown is one of the SEM images of an interlaced cuprous oxide microcubic material prepared in Example 1 of the present invention. It can be seen that the sample has an interlaced microcubic morphology and is grown and loaded on a porous copper foam substrate.

[0078] like Figure 3 The image shown is the second SEM image of an interlaced cuprous oxide micron-cubic material prepared in Example 1 of this invention. It can be seen that the sample has an interlaced micron-cubic morphology with a particle size of 1-2 μm.

[0079] like Figure 4 The image shown is the third SEM image of an interlaced cuprous oxide micron-cubic material prepared in Example 1 of this invention. It can be seen that the sample has an interlaced micron-cubic morphology and the surface of the cube is smooth and flat.

[0080] like Figure 5 As shown, the CV curve of an interleaved cuprous oxide micron-cubic material prepared in Example 1 of the present invention is shown. The curve has obvious redox peaks, and the corresponding current increases sequentially with the increase of scanning speed.

[0081] like Figure 6 The figure shows the GCD curve of an interleaved cuprous oxide micron-sized cubic material prepared in Example 1 of this invention. The discharge time decreases with increasing current density. At a current density of 5 mA / cm²... 2 At that time, the areal capacitance of the electrode was 1556 mF / cm². 2 .

[0082] like Figure 7 As shown, an interleaved cuprous oxide microcubic material prepared in Example 1 of this invention is subjected to a current density of 30 mA / cm². -2 Cyclic stability test curves were obtained. After 5000 cycles, the capacity retention was 94.2%.

[0083] like Figure 8 The image shown is a SEM image of an interlaced cuprous oxide micron-cubic material prepared in Example 2 of this invention. It can be seen that the sample has an interlaced micron-cubic morphology, with smooth cubic surfaces and uniform particle size.

[0084] like Figure 9 The image shown is a SEM image of an interlaced cuprous oxide micron-cubic material prepared in Example 3 of this invention. It can be seen that the sample has an interlaced micron-cubic morphology and the particle size is reduced.

[0085] like Figure 10 The image shown is a SEM image of an interlaced cuprous oxide microcubic material prepared in Example 4 of this invention. It can be seen that the sample has an interlaced microcubic morphology with increased interlacing degree.

[0086] like Figure 11 The image shown is a SEM image of an interlaced cuprous oxide microcubic material prepared in Example 5 of this invention. It can be seen that the sample has an interlaced microcubic morphology, with an increased number of interlaced cubes and a certain degree of stacking.

[0087] like Figure 12 The image shown is a SEM image of an interlaced cuprous oxide microcubic material prepared in Example 6 of this invention. It can be seen that the sample has an interlaced microcubic morphology, and the degree of interlacing is reduced.

Claims

1. An electrochemical preparation method for staggered cuprous oxide micron-sized cubes, characterized in that, The method includes the following steps: Step 1: Clean the cut foamed copper in acetone, hydrochloric acid and deionized water by ultrasonic cleaning in sequence. After wiping it dry, vacuum dry it at 50-60℃ for 3-6 hours. Step 2: Place the copper foam obtained in Step 1 in a mixed solution of alkaline solution and persulfate solution, wherein the molar ratio of hydroxide ions in the alkaline solution to persulfate ions in the persulfate solution is (100-200):

1. React at room temperature for 12-36 minutes, turning the copper foam over every 5-7 minutes. After the reaction is complete, wash the copper foam intermediate with deionized water and then vacuum dry it at 50-60°C for 3-6 hours. Step 3: Arrange the single layer of copper foam intermediate obtained in Step 2 in a ceramic boat, and calcine it in a muffle furnace at a heating rate of 2-10℃ / min to 190-230℃ for 1.5-3.5h. Step 4: Using a selenite solution of 14.4–54.1 mmol / L as the electrolyte, the copper foam obtained in Step 3 is electrochemically treated in a three-electrode system, followed by washing with deionized water and vacuum drying at 50–60 °C for 3–6 h to prepare interleaved cuprous oxide micron-cubic material loaded on a copper foam substrate.

2. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The specific operation of the drying process described in step 1 is as follows: the cleaned foam copper is arranged in a petri dish in sequence, and the accumulated moisture on its surface is absorbed with lens paper.

3. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The alkaline solution mentioned in step 2 is an aqueous solution of sodium hydroxide and / or potassium hydroxide.

4. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The persulfate mentioned in step 2 is one or a mixture of two or more of sodium persulfate, potassium persulfate, and ammonium persulfate.

5. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, In step 3, the temperature is raised to 200-210°C in a muffle furnace at a heating rate of 5-10°C / min, and calcined for 2.5-3.5 hours.

6. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The method for preparing the selenite solution in step 4 is as follows: add selenium dioxide to deionized water, with a mass ratio of selenium dioxide to deionized water of (0.0016 to 0.006): 1, and stir at room temperature for 20 to 35 minutes.

7. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The three-electrode system described in step 4 is as follows: the working electrode is the copper foam obtained in step 3, the counter electrode is a platinum sheet electrode, the reference electrode is an Ag / AgCl electrode, and the electrolyte is a selenite solution.

8. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 7, characterized in that, The three-electrode system described in step 4 is as follows: the working electrode is the copper foam obtained in step 3, and the counter electrode is 1.0*1.0cm. 2 The electrode is a platinum sheet, the reference electrode is an Ag / AgCl electrode, and the electrolyte is a 50 mL selenite solution.

9. The electrochemical preparation method of staggered cuprous oxide micron cubes according to claim 1, characterized in that, The parameters for the electrochemical treatment in step 4 are as follows: cyclic voltammetry scans are performed in a low voltage range of -1.3 to -1.0 V and a high voltage range of 0 to 0.3 V, with a scan rate of 3 to 10 mV s. -1 The number of scans is 2 to 6.

10. An interleaved cuprous oxide microcubic material prepared by the method according to any one of claims 1-9.

Images