Flexible copper-based material with multi-layer nanostructure and preparation method and application of flexible copper-based material
By preparing flexible copper-based materials with multi-layer nanostructures, the problem of difficulty in taking into account flexibility and catalytic performance of nanoporous materials is solved, and the combination of high flexibility and excellent catalytic performance is achieved. The industrial copper foil waste is effectively utilized, which reduces resource waste and preparation costs.
Patent Information
- Application Number
- CN202510326169.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-19
- Publication Date
- 2025-07-18
AI Technical Summary
Existing high flexibility nanoporous materials are difficult to take into account both flexibility and catalytic properties. Traditional nanoporous materials are prone to brittleness when used under special conditions and are seriously wasted resources.
By preparing flexible copper-based materials with multi-layer nanostructures, including copper-based metal layer, copper porous layer and oxide layer, dealloy treatment is used to form copper porous layer and thorn blade-like oxide layer, combined with controlling the dealloy solution and time, the material structure is regulated to take into account flexibility and catalytic properties.
It achieves that while maintaining high flexibility, the materials have excellent catalytic properties and effectively utilize industrial waste copper foil, reducing resource waste and preparation costs.
Smart Images
Figure CN120330779A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of metal catalytic materials, and particularly to a flexible copper-based material with a multi-layer nanostructure, a preparation method thereof, and an application thereof. Background Art
[0002] Nanoporous structured metal consists of a metal skeleton at the nanoscale and its pores. Therefore, nanostructured metal materials have broad application prospects in the fields of catalysis, filtration, sensors, heat exchange, drug delivery, etc. However, due to the existence of a large number of porous structures in traditional nanoporous materials, there are a large amount of stresses on the surface and inside of the materials, resulting in relatively brittle nanoporous structures and being unable to be used under some special conditions, such as in a narrow space where the nanoporous material needs to be twisted and bent to a certain extent. Therefore, the preparation of highly flexible nanoporous materials has become one of the hottest topics at present.
[0003] However, for nanoporous materials, their catalytic performance mainly depends on the pore structure. The increase in the number of pores will bring about an improvement in catalytic performance, but the more pores there are, the more the flexibility of the material will be sacrificed. Therefore, it is very difficult for highly flexible nanoporous materials to simultaneously take into account both flexibility and catalytic performance. Summary of the Invention
[0004] The purpose of the present invention is to provide a flexible copper-based material with a multi-layer nanostructure and a preparation method thereof to solve the problem that it is difficult for existing highly flexible nanoporous materials to simultaneously take into account both flexibility and catalytic performance. By regulating the formation of an oxide to form a multi-layer structure, the material not only has high flexibility but also excellent catalytic performance.
[0005] According to the first aspect of the purpose of the present invention, a flexible copper-based material with a multi-layer nanostructure is provided. The material includes a flexible matrix, and the flexible matrix has a multi-layer structure layer, and the multi-layer structure layer includes:
[0006] A first structure layer composed of a copper-based metal layer;
[0007] A second structure layer located on both sides of the copper-based metal layer, and the second structure layer is a copper porous layer; and
[0008] A third structure layer located on the copper porous layer, and the third structure layer is an oxide layer.
[0009] As an optional implementation manner, the copper porous layer has a nanoporous structure, and the nanoporous structure is formed by removing zinc in the matrix.
[0010] As an optional implementation manner, the oxide in the oxide layer is an oxide of zinc and has a thorn-leaf-shaped nanostructure.
[0011] As an alternative embodiment, the composition of the copper-based metal layer includes copper and zinc.
[0012] As an alternative embodiment, the thickness of the copper-based metal layer is 1 μm to 20 μm, the thickness of the copper porous layer is 0.5 μm to 1.5 μm, and the thickness of the oxide layer is 400 nm to 1000 nm.
[0013] As an alternative embodiment, the composition of the copper-based metal layer includes copper and zinc, and the oxide in the oxide layer is zinc oxide.
[0014] According to the second aspect of the object of the present invention, there is provided a method for preparing the foregoing flexible copper-based material with a multi-layer nanostructure, comprising the following steps:
[0015] Place the flexible copper-based metal foil with surface impurities removed in an alkaline solution, seal it, and perform dealloying treatment under the condition of a constant temperature water bath to obtain a flexible copper-based material with a nanostructure.
[0016] As an alternative embodiment, the thickness of the flexible copper-based metal foil is 10 μm to 20 μm.
[0017] As an alternative embodiment, the flexible copper-based metal foil contains copper and zinc, wherein the content of copper is 50 wt.% to 70 wt.%.
[0018] As an alternative embodiment, the conditions for dealloying are: perform dealloying treatment in a sodium hydroxide solution with a concentration of 0.1 M to 0.5 M for 48 h to 96 h under the water bath condition of 25°C.
[0019] According to the third aspect of the object of the present invention, there is provided an application of the foregoing flexible copper-based material with a multi-layer nanostructure in electrolyzed water.
[0020] As can be seen from the above technical solutions of the present invention, the flexible copper-based material with a multi-layer nanostructure proposed by the present invention controls the matrix material, combines the control of the dealloying solution and time, regulates the structure of the material, obtains different nanostructure layers, and retains part of the original matrix layer, so that while having excellent flexibility, the multi-layer nanostructure layers provide excellent catalytic performance;
[0021] The copper porous layer ensures the stable attachment of the surface nanostructure and the conduction of electrons, ions, etc., has a mass transfer, conductivity, and a small part of the catalytic effect. The special nanostructure of the thorns and leaves on the surface of the oxide layer provides a large number of active sites and has an efficient catalytic effect. After the efficient mass transfer and conductivity of the copper porous layer, the solution undergoes main catalysis through the thorns and leaves nanostructure of the oxide layer, thus ensuring the excellent catalytic performance of the material. Description of the Drawings
[0022] Figure 1 It is a schematic structural diagram of the flexible copper-based material with a multi-layer nanostructure of the present invention.
[0023] Figure 2 It is an SEM image of the sample of Example 1 of the present invention; wherein, A is a cross-sectional view, B is a partially enlarged view of the cross-section of B, and C is a surface view.
[0024] Figure 3 It is an SEM image of the sample of Example 3 of the present invention; wherein, A is a cross-sectional view and B is a partially enlarged view of the cross-section.
[0025] Figure 4 It is an SEM image of the sample of Comparative Example 1 of the present invention; wherein, A is a cross-sectional view and B is a partially enlarged view of the cross-section.
[0026] Figure 5 It is an SEM image of the sample of Comparative Example 2 of the present invention; wherein, A is a surface view at low magnification and B is a surface view at high magnification.
[0027] Figure 6 It is an SEM image of the sample of Comparative Example 3 of the present invention; wherein, A is a cross-sectional view and B is a partially enlarged view of the cross-section.
[0028] Figure 7 It is an SEM image of the sample of Comparative Example 4 of the present invention; wherein, A is a cross-sectional view and B is a partially enlarged view of the cross-section.
[0029] Figure 8 It is an SEM image of the sample of Comparative Example 5 of the present invention.
[0030] Figure 9 It is an SEM image of the sample of Comparative Example 6 of the present invention; wherein, A is a cross-sectional view and B is a partially enlarged view of the cross-section.
[0031] Figure 10 It is an LSV curve graph of the samples of Example 1 and Comparative Examples 1-6 of the present invention. Detailed Embodiments
[0032] For a better understanding of the technical content of the present invention, specific embodiments are hereby given and described in conjunction with the accompanying drawings as follows.
[0033] In the present disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which many illustrative embodiments are shown. The embodiments of the present disclosure are not necessarily intended to cover all aspects of the present invention. It should be understood that the various concepts and embodiments introduced above, as well as those concepts and embodiments described in more detail below, can be implemented in any of many ways.
[0034] The present invention forms an oxide composite nanoporous catalytic material by controlling selective dissolution and deposition reactions. This material has a heterostructure and exhibits the dual functions of a semiconductor-type oxide and a metal simultaneously. Its synergistic catalysis has a positive effect on improving catalytic performance. Moreover, the present invention can directly use industrial metal foil waste scraps as precursors to construct a metal catalytic material that takes into account both flexibility and catalytic performance.
[0035] Due to its own excellent physical properties, such as flexibility and electrical conductivity, metal foils are widely used in industries such as the chemical industry, electrical appliances, and precision instruments. However, during the industrial production process, due to product requirements, the produced metal foils are cut into specific shapes, resulting in a large amount of waste scraps that cannot be used, causing a great deal of waste in terms of resources and economy.
[0036] At present, one method for recycling metal waste is to recycle it, clean it, process it, remelt it, and then roll it. Another method is through chemical regeneration. First, the waste metal is dissolved as a whole, and then the required metal is precipitated by adding specific chemical reagents. The process is cumbersome and complex, and the cost is relatively high. The ineffective recycling of metal foils causes huge waste of resources.
[0037] Therefore, the present invention can also be used as a recycling technology for industrial copper foils, avoiding waste of resources, reducing the preparation cost of materials, and being environmentally friendly and economical.
[0038] Combined Figure 1 As shown, in an exemplary embodiment of the present invention, a flexible copper-based material with a multi-layer nanostructure is provided. This material includes a flexible matrix, and the flexible matrix has a multi-layer structure layer. The multi-layer structure layer includes:
[0039] A first structure layer 1 composed of a copper-based metal layer, and the composition of the copper-based metal layer includes copper and zinc;
[0040] A second structure layer 2 located on both sides of the copper-based metal layer. The second structure layer is a copper porous layer with a nanoporous structure, and the nanoporous structure is formed by removing zinc from the matrix; and
[0041] A third structure layer 3 located on the copper porous layer. The third structure layer is an oxide layer with a thorned leaf-shaped nanostructure, and the oxide of the oxide layer is an oxide of zinc.
[0042] It can be understood that this material takes the first structure layer as the starting layer. The second structure layer is provided on both sides of the first structure layer, and the third structure layer is provided on each second structure layer, forming a multi-layer structure with the first structure layer as the sandwich.
[0043] As an alternative example, the thickness of the copper-based metal layer is 1 μm to 20 μm, particularly preferably 5 μm or more. This layer mainly provides flexibility to the material.
[0044] As an alternative example, the thickness of the copper porous layer is 0.5 μm to 1.5 μm, particularly preferably 1 μm. This layer is for mass transfer, conduction, and a small part of the catalytic effect.
[0045] As an alternative example, the thickness of the oxide layer is 400 nm to 1000 nm. This layer plays a major catalytic role.
[0046] In another exemplary embodiment of the present invention, a method for preparing the foregoing flexible copper-based material with a multi-layer nanostructure is provided, including the following steps:
[0047] Place the flexible copper-based metal foil with surface impurities removed into an alkaline solution, seal it, and perform dealloying treatment under the condition of a constant temperature water bath to obtain a flexible copper-based material with a nanostructure.
[0048] As an alternative example, the thickness of the flexible copper-based metal foil is 10 μm to 20 μm. If the copper foil is too thick, the thickness of the original layer will correspondingly increase, the strength will increase, but the flexibility will decrease. Even if the dealloying time is increased to make the original layer thinner, the corresponding porous layer will thicken and the internal stress will also increase, with a risk of fracture.
[0049] As an alternative example, the flexible copper-based metal foil contains copper and zinc, where the copper content is 50 wt.% to 70 wt.%. For example, as shown in Table 1, copper foils of any one or more of the grades H65, H59, H62, and H68. If there is too little copper, the ductility and conductivity will decrease significantly, and it cannot be pressed into a foil; while if there is too much copper, it is difficult to form a porous skeleton, and it is difficult to form or there are very few thorn leaf-shaped nanostructures on the surface, and the catalytic performance will decrease significantly.
[0050] In a specific example, recycled industrial-grade copper foil scraps, H65 copper foil with a thickness of 10 μm to 20 μm, are used as the precursor.
[0051] Table 1 Brass foil grades and components
[0052] Grade Cu% Zn% Impurity% H59 57-60 Remainder ≤1 H62 60.5-63.5 Remainder ≤0.5 H65 63.5-68 Remainder ≤0.3 H68 67-70 Remainder ≤10.3
[0053] As an alternative example, under the water bath condition of 25 °C, place the H65 copper foil in a sodium hydroxide solution with a concentration of 0.1 M to 0.5 M for dealloying treatment for 48 h to 96 h. During the dealloying treatment of both sides of the copper foil, zinc is removed leaving a copper porous layer, and as time goes by, a thorn leaf-shaped nanostructure composed of zinc oxide is formed on the copper porous layer, and by controlling the dealloying time, a part of the original metal layer is retained.
[0054] In another exemplary embodiment of the present invention, there is also provided an application of the aforementioned flexible copper-based material with a multi-layer nanostructure in electrolyzed water.
[0055] The flexible copper-based material with a multi-layer nanostructure of the present invention can be applied to special structures and environments that require folding and bending. For example, the material can be folded and bent and then inserted into a certain structure for catalysis; or, multiple pieces of the material can be stacked and compacted for use.
[0056] It can be understood that due to the high flexibility of the material of the present invention, there is no special requirement for its shape, and the precursor can be of any shape.
[0057] For better understanding, the present invention will be further described below in conjunction with several specific examples. However, the preparation process is not limited thereto, and the content of the present invention is not limited thereto.
[0058] Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.
[0059] Example 1
[0060] A recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities, and then placed in 200 mL of 0.1 mol / L NaOH. Under the condition of a 25°C water bath, dealloying was carried out for 96 h to obtain a sample.
[0061] Example 2
[0062] A recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities, and then placed in 200 mL of 0.5 mol / L NaOH. Under the condition of a 25°C water bath, dealloying was carried out for 96 h to obtain a sample.
[0063] Example 3
[0064] A recycled industrial brass H65 foil with dimensions of 100×100×0.02 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities, and then placed in 200 mL of 0.1 mol / L NaOH. Under the condition of a 25°C water bath, dealloying was carried out for 96 h to obtain a sample.
[0065] Comparative Example 1
[0066] [Reduce the concentration of sodium hydroxide]
[0067] The recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 0.01 mol / L NaOH and subjected to dealloying for 96 h under the condition of a 25°C water bath to obtain the sample.
[0068] Comparative Example 2
[0069] [Increase the concentration of sodium hydroxide]
[0070] The recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 1 mol / L NaOH and subjected to dealloying for 12 h under the condition of a 25°C water bath to obtain the sample.
[0071] Comparative Example 3
[0072] [Reduce the dealloying time]
[0073] The recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 0.1 mol / L NaOH and subjected to dealloying for 6 h under the condition of a 25°C water bath to obtain the sample.
[0074] Comparative Example 4
[0075] [Increase the dealloying time]
[0076] The recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 0.1 mol / L NaOH and subjected to dealloying for 192 h under the condition of a 25°C water bath to obtain the sample.
[0077] Comparative Example 5
[0078] [Change the etching solution]
[0079] The recycled industrial brass H65 foil with dimensions of 100×100×0.01 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 0.1 mol / L HCl and subjected to dealloying for 96 h under the condition of a 25°C water bath to obtain the sample.
[0080] Comparative Example 6
[0081] [Change the thickness of the copper foil]
[0082] The recycled industrial brass H65 foil with dimensions of 100×100×0.05 mm was ultrasonically cleaned 3 times with deionized water and absolute ethanol to remove surface impurities. Then it was placed in 200 mL of 0.1 mol / L HCl and dealloyed for 96 h under a water bath condition at 25 °C to obtain the sample.
[0083] Test
[0084] [Morphology test]
[0085] The samples of Example 1 and Comparative Examples 1 - 6 were subjected to SEM testing, and the results are as Figure 2 and Figure 3 shown.
[0086] From Figure 2 and 3 it can be seen that the material prepared by the present invention has a multi - layer structure, with an original metal layer having a thickness of about 6.15 μm, and porous layers and thorn - leaf - shaped nanostructures on both sides of the original metal layer, with thicknesses of about 569 nm - 1.04 μm and 616 nm - 795 nm respectively.
[0087] Combined with Figure 4 and 5 it can be known that on the premise that other conditions remain unchanged, when changing the concentration of sodium hydroxide, when the concentration is too low, the growth rates of the oxide and the porous layer are extremely slow, and the thicknesses of the oxide and the porous layer cannot meet the requirements; when the concentration is too high, the oxide will dissolve. As Figure 5 shown, for the sample of Comparative Example 2, the zinc and zinc oxide on the surface were dissolved at 12 h, and even copper began to react to form granular cuprous oxide, and the required morphology could not be formed;
[0088] Combined with Figure 6 and 7 it can be known that on the premise that other conditions remain unchanged, when changing the dealloying time, when the dealloying time is too short or too long, the thicknesses of the oxide and the porous layer cannot meet the requirements. Especially when the time is too long, the oxide may dissolve. The growth rate in the early stage is greater than the dissolution rate, so it shows a growing morphology, but the mass transfer rate of the porous layer increases, resulting in a decrease in the contact area between sodium hydroxide and the underlying matrix, and a decrease in the local NaOH concentration during the reaction, leading to a decrease in the reaction rate, and the growth rate of the oxide decreases significantly. Therefore, the dissolution rate of the oxide is greater than the growth rate, and the phenomenon of a decrease in the oxide thickness occurs, and the required morphology cannot be obtained;
[0089] Combined with Figure 8 it can be known that on the premise that other conditions remain unchanged, when changing the corrosion solution, zinc dissolves in HCl, leaving copper to form porous copper, and no oxide is formed, and the required morphology cannot be obtained;
[0090] Combination Figure 9 It can be seen that on the premise that other conditions remain unchanged, by changing the thickness of the precursor, the desired morphology can be obtained;
[0091] As can be seen from the above, when the type and concentration of the dealloying solution change, or the dealloying time changes, the desired structure cannot be obtained.
[0092] [Flexibility Test]
[0093] The samples of Example 1 and Comparative Example 6 were subjected to a flexibility test. The results showed that the sample of Example 1 had excellent flexibility, could be easily bent by more than 90°, and could be bent more than 800 times. When bent at 180°, after 500 bends, it still did not break and still had good flexible properties.
[0094] The sample of Comparative Example 6 broke within 150 bends when bent at 180°.
[0095] [Electrolytic Water Catalytic Performance Test]
[0096] The surface of the sample was rinsed with deionized water and alcohol to remove the surface solution; the sample was welded to a nickel wire, and the welding point and the nickel wire were coated with an insulating resin and placed indoors for about 10 min. After the resin was slightly dried, the coated part could reach a good insulating state.
[0097] Then, its linear sweep voltammetry curve (LSV) was tested in 150 ml of 1 mol / L NaOH. Before the test, nitrogen was introduced into the NaOH solution for 30 min to remove the dissolved oxygen in the solution and eliminate its interference with the experiment; during the test, graphite was selected as the counter electrode, Ag / AgCl as the reference electrode, and the prepared material as the working electrode. Among them, the reference electrode and the working electrode were immersed in the NaOH solution electrolytic cell, Ag / AgCl was immersed in the saturated KCl solution electrolytic cell, and the two solution cells were connected by a salt bridge. The scanning potential of LSV was from -1.8 V to 1.2 V, and the whole test process was carried out under the condition of a 25°C water bath.
[0098] The results are as Figure 10 shown. At the same current density (-10 mA / cm 2 ), the overpotential corresponding to the sample of Example 1 was the lowest, indicating that the energy required for electrolysis was the lowest and the catalytic performance was the best.
[0099] As can be seen from the above, the material of the present invention has excellent catalytic performance while having high flexibility.
[0100] Although the present invention has been disclosed above in preferred embodiments, it is not intended to limit the present invention. Those of ordinary skill in the art to which the present invention pertains can make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to what is defined by the claims.
Claims
1. A flexible copper-based material with a multi-layer nanostructure, characterized in that, The material includes a flexible matrix, and the flexible matrix has a multi-layer structural layer, and the multi-layer structural layer includes: A first structural layer composed of a copper-based metal layer; Second structural layers located on both sides of the copper-based metal layer, and the second structural layers are copper porous layers; and A third structural layer located on the copper porous layer, and the third structural layer is an oxide layer.
2. The flexible copper-based material with a multi-layer nanostructure according to claim 1, characterized in that, The copper porous layer has a nanoporous structure, and the nanoporous structure is formed by removing zinc in the matrix.
3. The flexible copper-based material with a multi-layer nanostructure according to claim 1, characterized in that, The oxide of the oxide layer is an oxide of zinc and has a thorn-leaf-shaped nanostructure.
4. The flexible copper-based material with a multi-layer nanostructure according to claim 1, characterized in that, The composition of the copper-based metal layer includes copper and zinc.
5. The flexible copper-based material with a multi-layer nanostructure according to claim 1, characterized in that, The thickness of the copper-based metal layer is 1 μm to 20 μm, the thickness of the copper porous layer is 0.5 μm to 1.5 μm, and the thickness of the oxide layer is 400 nm to 1000 nm.
6. A method for preparing a flexible copper-based material with a multi-layer nanostructure according to any one of claims 1-5, characterized in that, It includes the following steps: Put the flexible copper-based metal foil with surface impurities removed into an alkaline solution, seal it, and perform dealloying treatment under the condition of a constant-temperature water bath to obtain a flexible copper-based material with a nanostructure.
7. The preparation method according to claim 6, characterized in that, The thickness of the flexible copper-based metal foil is 10 μm to 20 μm.
8. The preparation method according to claim 6, characterized in that, The flexible copper-based metal foil contains copper and zinc, and the content of copper is 50 wt.% to 70 wt.%.
9. The preparation method according to claim 6, characterized in that The conditions for dealloying are: perform dealloying treatment in a sodium hydroxide solution with a concentration of 0.1 M to 0.5 M for 48 h to 96 h under the water bath condition of 25°C.
10. Application of the flexible copper-based material with a multi-layer nanostructure according to any one of claims 1-5 in electrolyzed water.