A copper-gold complex nanowire film, and a preparation method and application thereof
The preparation of copper-gold complex nanowire films by self-assembly method solves the problems of easy detachment and difficulty in separation of nanowire powder, realizes low-cost and high-efficiency preparation of nanowire films, and enhances their application potential in catalysts, solar cells and energy storage devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHEJIANG UNIV OF TECH
- Filing Date
- 2024-02-01
- Publication Date
- 2026-08-04
AI Technical Summary
In existing technologies, nanowire powder is prone to detachment and is difficult to separate and recycle during application. Furthermore, there is no simple, low-cost, and controllable process for preparing copper-gold complex nanowire films, which limits their application in catalysts, solar cells, and energy storage devices.
Copper-gold complex nanowire films were prepared by a self-assembly method. A first precursor solution was formed by dissolving soluble copper salt, reducing agent and sodium dodecylbenzenesulfonate in water, and then reacted with a second precursor solution of potassium gold cyanide dissolved in water. The solid phase was collected, washed, centrifuged and dried to obtain the copper-gold complex nanowire film.
The large-scale, low-cost, green and efficient preparation of copper-gold complex nanowire films has been achieved with high yield, simple preparation process and good reproducibility. The nanowire films have excellent bending resistance, light transmittance and photoelectric properties, which broadens the application range.
Smart Images
Figure CN118062872B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of nanomaterial assembly technology, specifically to a copper-gold complex nanowire film, its preparation method, and its application. Background Technology
[0002] Metal nanowires possess excellent optoelectronic properties and a unique one-dimensional structure. The confinement and quantum size effects generated by this unique one-dimensional structure give them physical properties distinct from macroscopic materials. Nanowires exhibit excellent bending resistance and light transmittance, making them a promising alternative to traditional ITO conductive glass when fabricated into transparent conductive films.
[0003] Currently, the preparation methods for nanowires are relatively mature. However, current synthesis methods all produce powdered nanowires, which have limitations in application. For example, when used as catalysts, they are prone to detachment during reaction stirring, thus affecting catalytic performance, and the catalyst is difficult to separate and recover after the reaction. Fabricating nanowire powder into thin-film electrodes can effectively solve the problems of easy detachment and difficult separation and recovery. Furthermore, nanowire films are also used in solar cells or energy storage devices to improve device performance by enhancing light absorption or charge transport efficiency, greatly expanding their application range.
[0004] However, the process of fabricating nanowires into nanowire films is complex. For example, fabricating transparent conductive films from silver nanowires requires complex processes, including spraying, spin coating, screen printing, blade coating, and inkjet printing, to randomly distribute the silver nanowires onto a flexible film to obtain a transparent conductive film. Currently, there are no reports on methods for preparing copper-gold complex nanowire films through self-assembly. Fabricating copper-gold complex nanowire films using simple, low-cost, and controllable processes remains a challenge. Summary of the Invention
[0005] This application provides a copper-gold complex nanowire film, its preparation method, and its application. The copper-gold complex nanowire film is prepared by a self-assembly method. The process is simple, the reaction conditions are mild, and the reproducibility is good. It realizes the large-scale, low-cost, green, and efficient preparation of nanowire films and solves the problems existing in the prior art.
[0006] To achieve the above objectives, the present application adopts the following technical solution.
[0007] A first aspect of this application provides a method for preparing a copper-gold complex nanowire film, comprising:
[0008] A soluble copper salt, a reducing agent, and sodium dodecylbenzenesulfonate were dissolved in water to obtain the first precursor solution.
[0009] Potassium gold cyanide was dissolved in water to obtain the second precursor solution;
[0010] The second precursor solution was slowly added to the first precursor solution to carry out the self-assembly reaction. The solid phase was collected, washed, centrifuged, and dried to obtain a copper-gold complex nanowire film.
[0011] The first and second precursor solutions were mixed to carry out a self-assembly reaction. The solid phase was collected, washed, centrifuged, and dried to obtain a copper-gold complex nanowire film.
[0012] In some embodiments, the soluble copper salt includes any one or a mixture of copper chloride, copper nitrate, copper sulfate, and ammonium copper chloride.
[0013] In some embodiments, the reducing agent is any one of ascorbic acid, glucose, or sodium borohydride.
[0014] In some embodiments, the concentration of copper salt in the first precursor solution is 0.01~0.075 mmol / mL, the concentration of reducing agent is 0.001~0.02 mmol / mL, and the concentration of sodium dodecylbenzenesulfonate is 0.01~0.16 g / mL.
[0015] In some embodiments, the concentration of potassium gold cyanide solution in the second precursor solution is 0.005~0.1 mmol / mL.
[0016] In some implementations, the volume ratio of the first precursor liquid to the second precursor liquid is 5:(3~5).
[0017] In some embodiments, the addition rate of the second precursor solution is 2 to 4 mL / s.
[0018] In some embodiments, the temperature of the self-assembly reaction is 25°C to 0°C.
[0019] A second aspect of this application provides a copper-gold complex nanowire film prepared by the above-described preparation method.
[0020] A third aspect of this application provides the application of the aforementioned copper-gold complex nanowire film in drug delivery, transparent conductive films, or biosensors.
[0021] Compared with the prior art, the beneficial effects of this application are as follows:
[0022] This application employs a special material system to synthesize cyano-bridged self-assembled copper-gold complex nanowire films in one step via a liquid-phase method. The preparation process is simple, the reaction conditions are mild, the reproducibility is good, the yield is high, and the cost is low, which greatly reduces the difficulty of nanowire film formation and realizes the large-scale, low-cost preparation of copper-gold complex nanowire films.
[0023] The copper-gold complex nanowire film of this application is synthesized by self-assembly of copper-gold complex nanowires with uniform size distribution, diameter of 20-40 nanometers and length in the micrometer range, with the participation of sodium dodecyl sulfonate. It has a high specific surface area and good structural stability, and has excellent bending resistance, light transmittance and photoelectric properties, and has broad application prospects. Attached Figure Description
[0024] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 This is a photograph of the self-assembled copper-gold complex nanowire film precipitated in Example 1.
[0026] Figure 2 SEM images of the self-assembled copper-gold complex nanowire film of Example 1 are shown, where b is a cross-sectional view of the self-assembled film and a is a planar view of the self-assembled film.
[0027] Figure 3 This is the energy spectrum of the self-assembled copper-gold complex nanowire film of Example 1;
[0028] Figure 4 This is an FTIR comparison image of the self-assembled copper-gold complex nanowire film of Example 1 and sodium dodecylbenzenesulfonate;
[0029] Figure 5 These are XRD patterns of the self-assembled copper-gold complex nanowire films prepared at different temperatures in Examples 1-4;
[0030] Figure 6 These are planar SEM images of the self-assembled copper-gold complex nanowire films prepared at different temperatures in Examples 1-4; where a represents 100℃, b represents 80℃, c represents 60℃, and d represents 25℃. Detailed Implementation
[0031] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.
[0032] In the following description of this embodiment, the terms "including", "comprising", "having", and "containing" are all open-ended terms, meaning that they include but are not limited to.
[0033] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.
[0034] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.
[0035] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.
[0036] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.
[0037] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0038] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0039] In a first aspect, this application provides a method for preparing a copper-gold complex nanowire film, comprising:
[0040] Copper salt, reducing agent and sodium dodecylbenzenesulfonate were dissolved in water to obtain the first precursor solution;
[0041] Potassium gold cyanide was dissolved in water to obtain the second precursor solution;
[0042] The second precursor solution was slowly added to the first precursor solution to initiate a self-assembly reaction. The solid phase was collected, washed, centrifuged, and dried to obtain a copper-gold complex nanowire film. The copper-gold complex nanowire film was a cyano-bridged copper-gold complex nanowire film.
[0043] In this application, the soluble copper salt includes any one or a mixture of copper chloride, copper nitrate, copper sulfate, and ammonium copper chloride, with ammonium copper chloride being the preferred soluble copper salt.
[0044] In this application, sodium dodecylbenzenesulfonate participates in assembly as a surfactant and template agent, promoting the self-assembly reaction.
[0045] The reducing agent is used to reduce divalent copper ions to monovalent copper ions. The monovalent copper ions then undergo a coordination reaction with potassium gold cyanide to obtain copper-gold complex nanowires. Using sodium dodecylbenzenesulfonate as a film-forming template, sodium dodecylbenzenesulfonate participates in and promotes the self-assembly reaction, successfully preparing copper-gold complex nanowire films.
[0046] In the embodiments of this application, the reducing agent is any one of ascorbic acid, glucose, or sodium borohydride, preferably ascorbic acid.
[0047] In this application, the concentration of copper salt in the first precursor solution is preferably 0.01~0.075 mmol / mL, the concentration of reducing agent is preferably 0.001~0.02 mmol / mL, and the concentration of sodium dodecylbenzenesulfonate is preferably 0.01~0.16 g / mL; the concentration of potassium gold cyanide solution in the second precursor solution is 0.005~0.1 mmol / mL. This application prepares cyano-bridged copper-gold complex nanowire films by slowly adding the second precursor solution dropwise to the first precursor solution to carry out a self-assembly reaction, wherein the volume ratio of the first precursor solution to the second precursor solution is 5:(3~5), preferably 5:4.
[0048] The self-assembly reaction temperature is 25℃~100℃, within which copper-gold complex nanowire films can be formed, and the reaction time is preferably 1~2h. The addition rate of the second precursor solution is preferably 2~4mL / s, which can improve the uniformity of the copper-gold complex nanowires and facilitate the self-assembly formation of copper-gold complex nanowire films.
[0049] By selecting the above-mentioned concentration, volume ratio, and reaction temperature, this application achieves two advantages: firstly, the prepared copper-gold complex nanowires have a uniform size distribution, with a diameter of 20-40 nanometers and a length at the micrometer level, which is beneficial for self-assembly to obtain structurally stable copper-gold complex nanowire films; secondly, it is beneficial for improving the self-assembly efficiency of copper-gold complex nanowires and achieving a high yield of copper-gold complex nanowire films.
[0050] It should be noted that, in order to ensure the uniformity of the assembly units of the copper-gold complex nanowire film, namely the copper-gold complex nanowires, the second precursor solution needs to be slowly added dropwise to the first precursor solution.
[0051] In this application, the washing process includes cleaning the solid phase of the self-assembly reaction with pure water and anhydrous ethanol to remove residual unreacted substances. After washing, the detergent is removed by centrifugation, and the film is dried to obtain a copper-gold complex nanowire film. To improve the integrity and coherence of the copper-gold complex nanowire film, ultrasonic cleaning cannot be used in this application.
[0052] Secondly, this application provides a copper-gold complex nanowire film prepared by the above-mentioned preparation method. The copper-gold complex nanowire film of this application uses copper-gold complex nanowires as assembly units and sodium dodecylbenzenesulfonate as a film-forming template, exhibiting a high specific surface area and good structural stability, as well as excellent bending resistance, light transmittance, and photoelectric properties.
[0053] Thirdly, the copper-gold complex nanowire film of this application possesses excellent bending resistance, light transmittance, and photoelectric properties, making it suitable for use in transparent conductive films and biosensors, replacing traditional ITO glass. Furthermore, the copper-gold complex nanowire film can also serve as a drug delivery carrier for drug transport.
[0054] The present application will be further illustrated by the following examples.
[0055] Example 1
[0056] 0.5 mmol of ammonium copper chloride dihydrate, 0.3 mmol of ascorbic acid, and 2.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0057] Dissolve 0.1 mmol of K[Au(CN)2] in 20 mL of deionized water to obtain the second precursor solution;
[0058] Then, the second precursor solution was poured into the first precursor solution at a rate of 4 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 100 °C for 1 h. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0059] Example 2
[0060] 0.5 mmol of ammonium copper chloride dihydrate, 0.3 mmol of ascorbic acid, and 2.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0061] Dissolve 0.1 mmol of K[Au(CN)2] in 20 mL of deionized water to obtain the second precursor solution;
[0062] Then, the second precursor solution was poured into the first precursor solution at a rate of 4 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 80 °C for 2 hours. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0063] Example 3
[0064] 0.5 mmol of ammonium copper chloride dihydrate, 0.3 mmol of ascorbic acid, and 2.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0065] Dissolve 0.1 mmol of K[Au(CN)2] in 20 mL of deionized water to obtain the second precursor solution;
[0066] Then, the second precursor solution was poured into the first precursor solution at a rate of 4 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 60 °C for 4 h. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0067] Example 4
[0068] 0.5 mmol of ammonium copper chloride dihydrate, 0.3 mmol of ascorbic acid, and 2.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0069] Dissolve 0.1 mmol of K[Au(CN)2] in 20 mL of deionized water to obtain the second precursor solution;
[0070] Then, the second precursor solution was poured into the first precursor solution at a rate of 4 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at room temperature (25°C) for 8 hours. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70°C to obtain a self-assembled copper-gold complex nanowire film.
[0071] Example 5
[0072] 0.75 mmol of ammonium copper chloride dihydrate, 0.3 mmol of ascorbic acid, and 1.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0073] Dissolve 0.2 mmol of K[Au(CN)2] in 25 mL of deionized water to obtain the second precursor solution;
[0074] Then, the second precursor solution was poured into the first precursor solution at a rate of 3 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 100 °C for 1 h. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0075] Example 6
[0076] 1.75 mmol of ammonium copper chloride dihydrate, 0.5 mmol of ascorbic acid, and 4 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0077] Dissolve 2 mmol of K[Au(CN)2] in 20 mL of deionized water to obtain the second precursor solution;
[0078] Then, the second precursor solution was poured into the first precursor solution at a rate of 5 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 100 °C for 1 h. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0079] Example 7
[0080] 0.5 mmol of ammonium copper chloride dihydrate, 0.025 mmol of ascorbic acid, and 2.0 g of sodium dodecylbenzenesulfonate were dissolved in 25 mL of deionized water and stirred magnetically to form a milky white first precursor solution.
[0081] Dissolve 0.1 mmol of K[Au(CN)2] in 15 mL of deionized water to obtain the second precursor solution;
[0082] Then, the second precursor solution was poured into the first precursor solution at a rate of 4 mL / s, and the mixture was stirred for 3 minutes. The mixture was reacted at 100 °C for 1 h. The resulting solid product was washed and extracted twice with pure water, and finally washed with anhydrous ethanol to remove residual water. The product was then centrifuged and dried in an oven at 70 °C to obtain a self-assembled copper-gold complex nanowire film.
[0083] In Example 1, the self-assembled copper-gold complex nanowire film was prepared, and its precipitate is shown in the following image. Figure 1 As shown, unlike conventional nanopowders, it has a film-like morphology.
[0084] The self-assembled copper-gold complex nanowire films prepared in the embodiments of this application were evaluated as follows:
[0085] 1. The self-assembled copper-gold complex nanowire film prepared in Example 1 was subjected to SEM testing, and the results are as follows: Figure 2 As shown. Figure 2 Image b shows a cross-sectional view of the self-assembled copper-gold complex nanowire film, and image a shows a planar view of the film. The planar view shows that the copper-gold complex nanowires are the assembly units, with a uniform size distribution, a diameter of 20-40 nanometers, and a length on the micrometer scale. The cross-sectional view shows...
[0086] Example 1 successfully prepared a structurally stable copper-gold complex nanowire film.
[0087] 2. Energy dispersive spectroscopy (EDS) was performed on the self-assembled copper-gold complex nanowire film prepared in Example 1, and the results are as follows: Figure 3 As shown. From Figure 3 It can be seen that, in addition to the five elements Au, Cu, C, N and O present in the nanowires themselves, the self-assembled copper-gold complex nanowire film also contains S and Na elements, indicating that sodium dodecylbenzenesulfonate participated in the assembly as a template agent.
[0088] 3. The self-assembled copper-gold complex nanowire film of Example 1 was subjected to Fourier transform infrared (FTIR) spectroscopy, and the results are as follows: Figure 4 As shown. From Figure 4 It can be seen that the characteristic peak at wavelength 2210 is unique to cyano, and the characteristic peak unique to sodium dodecylbenzenesulfonate in the infrared spectrum is also reflected in the infrared spectrum of the nanowire film. Figure 4 The results were consistent with the energy dispersive spectroscopy results of the self-assembled copper-gold complex nanowire film in Example 1, proving that sodium dodecylbenzenesulfonate participated in the assembly process of the copper-gold complex nanowire film.
[0089] 4. XRD and SEM tests were performed on the self-assembled copper-gold complex nanowire films prepared in Examples 1-4 to evaluate the copper-gold complex nanowire films prepared under different self-assembly temperature gradients. The self-assembly temperature of Example 1 was 100℃, the self-assembly temperature of Example 2 was 80℃, the self-assembly temperature of Example 3 was 60℃, and the self-assembly temperature of Example 4 was 25℃. Figure 5 For XRD test results, from Figure 5 It can be seen that the copper-gold complex nanowire films prepared at different temperatures are of the same phase, proving that the preparation method of this application has high reproducibility and good stability. Figure 6 SEM images of copper-gold complex nanowire films prepared by self-assembly at different temperatures under different scanning parameters. Figure 6 It can be seen that the copper-gold complex nanowire film is based on copper-gold complex nanowires as the basic unit; the copper-gold complex nanowires are uniform in size, all at the nanoscale, with a diameter of about 30 nanometers and a length at the micrometer level, and the copper-gold complex nanowires self-assemble to form the film.
[0090] Examples 5-7 all successfully prepared self-assembled copper-gold complex nanowire films after testing.
[0091] Although this application has been described in detail in this specification with general descriptions and specific embodiments, some modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, such modifications or improvements made without departing from the spirit of this application are all within the scope of protection claimed in this application.
Claims
1. A method for preparing a copper-gold complex nanowire film, characterized in that, include: A soluble copper salt, a reducing agent, and sodium dodecylbenzenesulfonate were dissolved in water to obtain the first precursor solution. Potassium gold cyanide was dissolved in water to obtain the second precursor solution; The second precursor solution was slowly added to the first precursor solution to carry out the self-assembly reaction. The solid phase was collected, washed, centrifuged and dried to obtain the copper-gold complex nanowire film. In the first precursor solution, the concentration of soluble copper salt is 0.01~0.075 mmol / mL, the concentration of reducing agent is 0.001~0.02 mmol / mL, and the concentration of sodium dodecylbenzenesulfonate is 0.01~0.16 g / mL; In the second precursor solution, the concentration of potassium gold cyanide solution is 0.005~0.1 mmol / mL; The volume ratio of the first precursor liquid to the second precursor liquid is 5:(3~5); The temperature for the self-assembly reaction is 25℃~100℃.
2. The method for preparing copper-gold complex nanowire films according to claim 1, characterized in that, The soluble copper salt includes any one or a mixture of copper chloride, copper nitrate, copper sulfate, and ammonium copper chloride.
3. The method for preparing copper-gold complex nanowire films according to claim 1, characterized in that, The reducing agent is any one of ascorbic acid, glucose, or sodium borohydride.
4. The method for preparing copper-gold complex nanowire films according to claim 1, characterized in that, The addition rate of the second precursor solution is 2~4 mL / s.
5. The copper-gold complex nanowire film prepared by the method of any one of claims 1-4.
6. The application of the copper-gold complex nanowire film according to claim 5 in drug delivery, transparent conductive films or biosensors.