Preparation method for regulating and controlling growth of hydrophobic Cu2S nanowire material on surface of copper foil
By treating and regulating the reaction on the copper foil surface, hydrophobic Cu2S nanowires were prepared, which solved the problem of insufficient hydrophobicity on the copper foil surface, achieved good photothermal properties and anti-fouling and anti-corrosion properties, and was suitable for industrial production.
Patent Information
- Application Number
- CN202510801567.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-07
- Publication Date
- 2025-09-23
AI Technical Summary
Existing technologies make it difficult to effectively control the growth of hydrophobic Cu2S nanowire materials on the surface of copper foil, resulting in insufficient photothermal properties and anti-fouling and anti-corrosion performance.
After the copper foil surface is treated, NaOH and ammonium persulfate solution are reacted, and then it is immersed in a silane coupling agent and reacted in a Na2S solution to regulate the growth of Cu2S nanowires and form a hydrophobic surface.
The simple preparation of hydrophobic Cu2S nanowires on the copper foil surface has been achieved. It has good photothermal properties and anti-fouling and anti-corrosion properties, and is suitable for large-scale industrial production.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of solid surfaces, in particular to a method for preparing a hydrophobic Cu2S nanowire material capable of controlled growth on a copper foil surface. Background Art
[0002] Wettability, a key property of solid surfaces, is primarily determined by both the surface roughness and chemical composition. Over the past two decades, research on hydrophobic surfaces has garnered significant attention, given the increasing importance of solid surfaces with exceptional wettability in industrial and agricultural production and daily life. Furthermore, hydrophobic surfaces are widely used in self-cleaning, corrosion prevention, anti-icing, and oil-water separation applications.
[0003] With the continued development of nanomaterials, semiconductor nanomaterials have been extensively researched. Cuprous sulfide, in particular, has attracted considerable attention due to its excellent photothermal properties and narrow semiconductor band gap. In solid-liquid interfacial reactions, the micro- and nanostructures of the solid surface and its wettability significantly influence its performance. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for preparing hydrophobic Cu2S nanowire material by controlling the growth on the surface of copper foil, so as to solve the shortcomings of the above-mentioned prior art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface, comprising the following steps: reacting the treated copper foil in a NaOH solution and an ammonium persulfate solution for 10 to 30 minutes, removing the copper foil, washing it with anhydrous ethanol, and drying it in an oven for 10 to 30 minutes; then soaking the resulting sample in a 2.5% to 10% silane coupling agent, KH-570 (γ-methacryloxypropyltrimethoxysilane), for 20 to 60 minutes. The pH is adjusted to 3-4 using oxalic acid. The resulting sample is then reacted in a 0.1 to 1 mol / L Na2S solution for 10 to 30 minutes, removed, and further soaked in the silane coupling agent for 20 to 60 minutes, thereby forming hydrophobic Cu2S nanowires on the copper foil surface.
[0006] Preferably, the copper foil is treated as follows: 1) cleaned with anhydrous ethanol and deionized water; 2) then treated with nitric acid and ultrasonically cleaned for 10 to 30 minutes; 3) then cleaned with ethanol and deionized water for 2 to 10 minutes after treatment, and finally dried.
[0007] Preferably, the volume ratio of the NaOH solution to the ammonium persulfate solution is 1-2:1, the concentration of the Na2S solution is 0.1-1 mol / L, and the silane coupling agents of different mass concentration ratios in step S1 are 2.5%-10%.
[0008] Preferably, the copper foil material has a thickness of 0.1 to 0.5 mm and a purity of 95.00% to 99.99%.
[0009] Preferably, the silane coupling agent is KH-550, KH-560 and KH-570.
[0010] Preferably, the pH adjusting agent is citric acid, oxalic acid and acetic acid.
[0011] Preferably, the diameter of the obtained hydrophobic Cu2S nanowires is 100-300 nm, and the air contact angle of the hydrophobic Cu2S nanowires is 91.64°-129.46°.
[0012] A surface-grown hydrophobic Cu2S nanowire material is constructed based on the preparation method of a copper foil surface-controlled hydrophobic Cu2S nanowire material as described in any one of claims 1-7, and is characterized in that it includes surface-grown hydrophobic Cu2S nanowires and a surface-loaded Cu2S nanowire structure.
[0013] In the above technical solution, the present invention provides a method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface: 1. The surface of the cuprous sulfide material of the present invention is hydrophobic, and has good application prospects in photothermal therapy, photothermal antibacterial, etc., and can prevent the surface of the material from being contaminated and corroded.
[0014] 2. The preparation method provided by this invention features simple processing and mild conditions, offering a novel approach for the large-scale production of hydrophobic cuprous sulfide nanowires. Compared to complex fluorinated reagents currently available, silane coupling agents offer the advantages of low cost and green chemistry. Compared to heating methods, silane coupling agents offer the advantages of mild conditions and can be obtained in large quantities at room temperature. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments described in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.
[0016] Figure 1 This is a SEM image of the Cu2S nanowires prepared in Example 1 of the present invention; Figure 2 This is a SEM image of Cu2S nanowires prepared in Example 2 of the present invention; Figure 3 This is a SEM image of Cu2S nanowires prepared in Example 3 of the present invention; Figure 4This is a SEM image of Cu2S nanowires prepared in Example 4 of the present invention; Figure 5 is the static contact angle of the surface of the Cu2S nanowire prepared in Example 1 of the present invention to water; Figure 6 is the static contact angle of the surface of the Cu2S nanowires prepared in Example 4 of the present invention to water. DETAILED DESCRIPTION
[0017] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings.
[0018] See also Figure 1-6 The present invention provides a method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface, comprising the following steps: 1) reacting the treated copper foil in a NaOH solution and an ammonium persulfate solution for 10-30 minutes, removing the copper foil, rinsing it with anhydrous ethanol, and drying it in an oven for 10-30 minutes. 2) soaking the resulting sample in a 2.5%-10% silane coupling agent, KH-570 (γ-methacryloxypropyltrimethoxysilane), for 20-60 minutes. Adjusting the pH to 3-4 with oxalic acid. 3) reacting the sample obtained in 2) in a 0.1-1 mol / L Na2S solution for 10-30 minutes, removing the sample, and continuing to soak it in the silane coupling agent for 20-60 minutes to form hydrophobic Cu2S nanowires on the copper foil surface.
[0019] According to the above scheme, the copper foil material in step 1 has a thickness of 0.1 to 0.5 mm and a purity of 95.00% to 99.99%. The volume ratio of the NaOH solution to the ammonium persulfate solution is 1-2:1, the concentration ratio of the NaOH solution is 4 to 1 mol / L, and the concentration ratio of the ammonium persulfate solution is 0.1 to 1 mol / L.
[0020] According to the above scheme, the silane coupling agent with different mass concentration ratios in step 2 is 2.5% to 10%.
[0021] According to the above scheme, the concentration of the Na2S solution in step 3 is 0.1 to 1 mol / L.
[0022] According to the above scheme, the reaction time in step 1 is 10 to 30 minutes. If the reaction time is too short, the nanowires grow sparsely. If the reaction time is too long, the nanowires grow stably and no longer change with time.
[0023] According to the above scheme, the soaking time in step 2 is 20 to 60 minutes. If the soaking time is too short, the nanowire modification phenomenon is not obvious. If the soaking time is too long, the modification effect is stable and no longer changes with time.
[0024] According to the above scheme, the reaction time of the Na2S solution in step 3 is 10 to 30 minutes. If the reaction time is too short, the reaction is incomplete. If the reaction time is too long, the formation of nanowires is affected, and the nanowires are easily agglomerated or large particles are formed.
[0025] The present invention also includes applications of the above-mentioned cuprous sulfide material with surface hydrophobicity in photothermal therapy, photothermal antibacterial therapy, photothermal water evaporation, and the like.
[0026] The method of the present invention obtains Cu2S nanowires by constructing on the surface of copper foil, and then obtains Cu2S nanowires with surface hydrophobicity through hydrophobic treatment. The hydrophobic treatment only requires simple steps, simple operation, mild conditions, low cost and is suitable for large-scale industrial production.
[0027] Specific embodiments are as follows: Example 1: 1-1 Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide pieces and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was ultrasonically cleaned in a 2 mol / L nitric acid solution for 10 to 30 minutes.
[0028] 1-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution is clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse with deionized water and then ethanol. Dry in air at 60°C for 10–30 minutes. This yields a Cu(OH)2@Cu foil with a blue film on its surface.
[0029] 1-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent KH570 to this solution and stir thoroughly. Adjust the pH to 3-4 with oxalic acid. Immerse copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH570-OA-10%.
[0030] Example 2: 2-1 Copper foil (0.3 mm thick, 99.9% purity) was cut into pieces 1 cm long and 1 cm wide. The copper foil was ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was ultrasonically cleaned in a 2 mol / L nitric acid solution for 10 to 30 minutes.
[0031] 2-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution is clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on its surface.
[0032] 2-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent to this solution and stir thoroughly. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and react in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH570-OA-5%.
[0033] Example 3: 3-1: Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide sections and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was ultrasonically cleaned in a 2 mol / L nitric acid solution for 10–30 minutes.
[0034] 3-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0035] 3-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent to this solution and stir thoroughly. Adjust the pH to 3-4 with oxalic acid. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is designated H570-OA-2.5%.
[0036] Example 4: 3-1: Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide sections and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was ultrasonically cleaned in a 2 mol / L nitric acid solution for 10–30 minutes.
[0037] 3-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0038] 3-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent to this solution and stir thoroughly. Adjust the pH to 3-4 with acetic acid. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH570-HAC-2.5%.
[0039] Example 5: 3-1: Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide sections and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was then ultrasonically cleaned in a 2 mol / L nitric acid solution for 10–30 minutes.
[0040] 3-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0041] 3-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent to this solution and stir thoroughly. Adjust the pH to 3-4 with citric acid. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH570-CA-2.5%.
[0042] Example 6: 3-1: Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide pieces and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was then ultrasonically cleaned in a 2 mol / L nitric acid solution for 10 to 30 minutes.
[0043] 3-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0044] 3-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add silane coupling agent KH-550 to this solution at a 10% mass ratio and stir thoroughly. Adjust the pH to 3-4 with oxalic acid. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH550-CA-2.5%.
[0045] Example 7: 3-1: Copper foil (0.3 mm thick, 99.9% purity) was cut into 1 cm long and 1 cm wide pieces and ultrasonically cleaned once with ethanol and once with deionized water, respectively. The cleaned copper foil was then ultrasonically cleaned in a 2 mol / L nitric acid solution for 10 to 30 minutes.
[0046] 3-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0047] 3-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent KH-560 to this solution and stir thoroughly. Adjust the pH to 3-4 with oxalic acid. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and obtain the modified Cu(OH)2 nanowires. React in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH560-CA-2.5%.
[0048] Based on the above scheme, this scheme also includes a comparative example, as follows: 4-1. Cut copper foil (0.3 mm thick, 99.9% purity) into a shape of 1 cm long and 1 cm wide. Ultrasonic cleaning is performed with ethanol and deionized water, respectively. The cleaned copper foil is then ultrasonically cleaned in a 2 mol / L nitric acid solution for 10 to 30 minutes.
[0049] 4-2 Prepare a 2 mol / L NaOH solution and a 0.125 mol / L ammonium persulfate solution until the solution becomes clear and transparent. First, measure 2 mL of the NaOH solution into a small beaker. Then, measure 2 mL of the ammonium persulfate solution and add it dropwise to the NaOH solution until it is evenly mixed. Then, use tweezers to completely immerse the copper foil in the evenly mixed solution. After 10–30 minutes, rinse it with deionized water and then ethanol. Dry it in air at 60°C for 10–30 minutes. This will produce a Cu(OH)2@Cu copper foil with a blue film on the surface.
[0050] 4-3 Prepare a solution with a mass ratio of 9:1 ethanol:water. Add 10% silane coupling agent to this solution and stir thoroughly. Immerse the copper foil in the 10% silane coupling agent for 20-60 minutes. Remove and react in a fixed Na2S solution at a concentration of 0.5 mol / L for 10-30 minutes. After reaction, return the foil to the silane coupling agent solution and continue reacting for 20-60 minutes. The sample is named KH570-CA-0%.
[0051] Therefore, combined with Figure 1-3 It can be seen from Examples 1-7 and Comparative Examples that the SEM morphology of Cu2S nanowires modified with silane coupling agents at mass concentrations of 10%, 5%, and 2.5% is relatively viscous. The specific structure of the modified material is as follows: Figure 1-4 It can be seen that the particles on the surface of Cu2S nanowires are larger and have a more viscous surface than before modification.
[0052] The contact angle test results of the material are as follows Figure 5-6 As can be seen, the contact angle of Cu2S nanowires gradually increases with increasing silane coupling agent concentration, and the material transitions from hydrophilic to hydrophobic. The contact angles at 0% and 10% concentrations are 75.62° and 129.45°, respectively. At a concentration of 10%, the contact angle is 129.45°, indicating strong hydrophobicity.
[0053] The above description is merely illustrative of certain exemplary embodiments of the present invention. It goes without saying that those skilled in the art will be able to modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and description are illustrative in nature and should not be construed as limiting the scope of protection of the claims.
Claims
1. A method for preparing hydrophobic Cu2S nanowire material grown on a copper foil surface, characterized in that: The steps include: S1. The copper foil material is treated and cleaned, and the treated copper foil is immersed in a 1.0-4.0 mol / L NaOH solution and a 0.10-0.2 mol / L ammonium persulfate solution for 10-30 minutes; the Cu(OH)2 nanowires with a blue film on the surface of the copper foil are removed and washed with anhydrous ethanol, and then dried in an oven at 60°C for 10-30 minutes. The sample is taken out and immersed in a 2.5%-10% silane coupling agent KH-570 for 20-60 minutes; and the pH is adjusted to 3-4 with oxalic acid; S2. Take out the sample obtained in step S1 and soak it in a 0.1-1.0 mol / L Na2S solution; after taking it out, continue soaking it in a silane coupling agent for 20-60 minutes to obtain hydrophobic Cu2S nanowires on the surface of the copper foil.
2. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The copper foil in S1 is processed as follows: 1) Clean with anhydrous ethanol and deionized water; 2) Then use nitric acid to perform ultrasonic cleaning for 10 to 30 minutes; 3) After treatment, rinse with ethanol and deionized water for 2 to 10 minutes and finally dry.
3. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The volume ratio of the NaOH solution to the ammonium persulfate solution is 1-2:1, the concentration of the Na2S solution is 0.1-1 mol / L, and the silane coupling agents of different mass concentration ratios in step S1 are 2.5%-10%.
4. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The thickness of the copper foil material is 0.1 to 0.5 mm, and the purity is 95.00% to 99.99%.
5. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The silane coupling agents are KH-550, KH-560 and KH-570.
6. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The pH adjusting reagents are citric acid, oxalic acid and acetic acid.
7. The method for preparing a hydrophobic Cu2S nanowire material grown on a copper foil surface according to claim 1, characterized in that: The diameter of the obtained hydrophobic Cu2S nanowires is 100-300 nm, and the air contact angle of the hydrophobic Cu2S nanowires is 91.64°-129.46°.
8. A surface-grown hydrophobic Cu2S nanowire material, constructed based on the preparation method of a copper foil surface-grown hydrophobic Cu2S nanowire material according to any one of claims 1 to 7, characterized in that: It includes surface-grown hydrophobic Cu2S nanowires and surface-loaded Cu2S nanowire structures.
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