Copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration and a method of preparing the same

Abstract

The application discloses a kind of copper sulfide with natural butterfly wing three-dimensional hierarchical configuration and its preparation method in the technical field of nanomaterials, the material is butterfly wing as biological template, after activation by pretreatment, sequentially carry out copper ion immersion and sulfur ion treatment to form seed crystal, finally under the induction of surfactant, hydrothermal reaction is prepared.Among them, two kinds of special surfactants are used: allyl ether modified epoxy phosphate surfactant is prepared by epoxy ring opening and phosphorylation reaction, trisiloxane polyether phosphate surfactant is prepared by hydrosilation and phosphorylation reaction.The application successfully replicates the unique three-dimensional hierarchical porous structure of butterfly wing, and the obtained copper sulfide material has high specific surface area and abundant active sites, and exhibits excellent performance in photocatalytic degradation and electrochemical energy storage, and the preparation process is green and economical, suitable for large-scale production.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, specifically to a copper sulfide with a three-dimensional hierarchical structure resembling natural butterfly wings and its preparation method. Background Technology

[0002] Copper sulfide, as an important p-type semiconductor material, shows broad application prospects in photoelectric conversion, catalytic degradation, and energy storage. Traditional copper sulfide preparation methods, such as hydrothermal methods, hot-injection methods, and conventional template methods, while capable of producing copper sulfide materials with different morphologies, generally suffer from insufficient morphology control precision, poor structural stability, complex processes, and the use of toxic reagents. In particular, copper sulfide materials prepared by conventional methods often have limited specific surface area, insufficient active sites, and are prone to aggregation, severely affecting their performance in photocatalysis and electrochemical applications. Furthermore, existing methods still have significant limitations in precisely controlling the microstructure of materials, making it difficult to achieve controllable preparation of hierarchical porous structures, which greatly restricts the performance of copper sulfide materials in practical applications.

[0003] In recent years, biotemplating has attracted widespread attention as an emerging material preparation method. This method utilizes the intricate biological structures evolved over long periods in nature as templates to prepare functional materials with multi-level ordered structures. Butterfly wings, as a typical biotemplate, possess a unique three-dimensional hierarchical porous structure, high specific surface area, and good mechanical stability, providing an ideal microscopic framework structure for functional materials. However, directly using butterfly wing templates suffers from problems such as insufficient active sites, high surface energy leading to easy aggregation, and weak binding force with inorganic materials. Although there are reports on the preparation of functional materials using butterfly wing templates in existing technologies, there are still significant shortcomings in the selection and use of surfactants. Commonly used commercial surfactants such as hexadecyltrimethylammonium bromide and sodium dodecyl sulfate have limited functionality and control precision, making it impossible to achieve precise control over the material morphology and fully utilize the structural advantages of butterfly wing templates.

[0004] To address the shortcomings of existing technologies, there is an urgent need to develop novel surfactant systems and improved preparation processes to fully utilize the unique structural advantages of butterfly wing templates and prepare copper sulfide materials with precisely regulated three-dimensional hierarchical structures. This invention innovatively develops two novel surfactants: allyl ether-modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant, successfully solving the problems of single-function surfactants and insufficient control precision in existing technologies. These two surfactants can work synergistically to precisely guide the growth of copper sulfide crystals at the molecular level, while ensuring the green, environmentally friendly, and economically feasible preparation process, providing a new technical route for the preparation of high-performance copper sulfide materials. Summary of the Invention

[0005] The purpose of this invention is to provide a copper sulfide with a natural butterfly wing three-dimensional hierarchical structure and its preparation method, which solves the technical problems of limited specific surface area, insufficient active sites, low morphology control precision and poor structural stability of existing copper sulfide materials.

[0006] The present invention achieves the above objectives through the following technical solutions:

[0007] A method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure, comprising the following steps:

[0008] S1. Soak the butterfly wings in an ethanol solution at room temperature, then wash them with distilled water and let them air dry. Place the dried butterfly wings in an ethylenediaminetetraacetic acid solution and pretreat them at 80-150℃.

[0009] S2, then cleaned and dried with solvent; the pretreated butterfly wings were placed in a copper ion solution and soaked at 30-80℃, then cleaned with ethanol; the copper-loaded butterfly wings were immersed in a sulfide ion solution at room temperature to form CuS seed crystals;

[0010] S3. Place the butterfly wing loaded with CuS seed crystals back into the copper ion solution, add thiourea, allyl ether modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant, transfer the reaction system to a high-pressure reactor, and react at a constant temperature of 100-180℃.

[0011] According to a preferred embodiment of the present invention, the butterfly wing template is a butterfly wing with a clear, complete and regular three-dimensional hierarchical micro-nano structure.

[0012] According to a preferred embodiment of the present invention, the copper source is selected from at least one of copper sulfate, copper chloride, and copper nitrate.

[0013] According to a preferred embodiment of the present invention, the sulfide ion solution is a Na2S or K2S solution.

[0014] In this invention, the preparation of copper sulfide with a natural three-dimensional hierarchical structure of butterfly wings is a crystal growth process based on a biotemplate method and surfactant-induced growth. The reaction mechanism involves multiple stages of chemical and physical processes. First, the butterfly wing template undergoes a pretreatment activation process. The carboxyl functional groups in the ethylenediaminetetraacetic acid (EDTA) solution form coordination bonds with biomolecules on the butterfly wing surface, while simultaneously removing surface impurities and lipids, exposing more active sites. This pretreatment process significantly enhances the surface activity and adsorption capacity of the butterfly wing template, providing a good foundation for subsequent metal ion adsorption. Heating helps EDTA molecules better penetrate the hierarchical porous structure of the butterfly wing and form stable complexes with biomacromolecules such as chitin, thereby effectively modifying the template surface. In the seed crystal formation stage, the pretreated butterfly wing template is immersed in a copper ion solution. The copper ions in the solution are adsorbed onto the active sites on the butterfly wing surface through coordination. The unique three-dimensional hierarchical porous structure of the butterfly wing template provides a large number of adsorption sites for copper ions, and its micron- and nano-scale hierarchical pore structure ensures the uniform distribution of copper ions. When immersed in a sulfide ion solution, the adsorbed copper ions react with the sulfide ions to form copper sulfide nuclei on the surface of the butterfly wings. These nuclei serve as seeds for subsequent crystal growth, and their distribution density and uniformity directly determine the morphology of the final product. Room temperature reaction conditions are beneficial for controlling the formation rate of nuclei, avoiding excessively rapid reactions that could lead to nuclei agglomeration or uneven distribution. The final hydrothermal reaction stage is the key step in the entire preparation process. The seeded butterfly wings are reinserted into the reaction system, thiourea is added as a sulfur source, and two specially formulated surfactants are introduced. Under hydrothermal conditions, thiourea gradually decomposes to release sulfide ions, which react with copper ions in the solution to form copper sulfide. The two surfactants work synergistically: the allyl ether-modified epoxy phosphate surfactant regulates the crystal growth direction through its phosphate groups interacting with the crystal surface; while the trisiloxane polyether phosphate surfactant, through its special trisiloxane structure, reduces interfacial tension and guides the crystals to grow epitaxially along the three-dimensional structure of the butterfly wing template. The high-temperature, high-pressure hydrothermal environment promoted the oriented growth and self-assembly of copper sulfide crystals, ultimately forming a copper sulfide material that perfectly replicates the three-dimensional hierarchical structure of butterfly wings. This unique structure not only maintains the fine morphological characteristics of the butterfly wing template but also endows the material with excellent physicochemical properties, laying the foundation for its applications in photocatalysis, energy storage, and other fields. The entire preparation process embodies a perfect combination of the bio-templating method and surfactant-induced crystal growth, demonstrating excellent controllability and reproducibility.

[0015] According to a preferred embodiment of the present invention, in step S1, the pretreatment time at 80-150°C is 2-6 hours.

[0016] According to a preferred embodiment of the present invention, in step S2, the soaking time at 30-80°C is 2-6 hours.

[0017] According to a preferred embodiment of the present invention, the preparation method of the allyl ether modified epoxy phosphate surfactant includes: A1, adding bisphenol A type epoxy resin, butyl acetate and n-butanol to a four-necked flask, heating to 58-62°C and stirring; adding allyl glycidyl ether and reacting it under the action of boron trifluoride diethyl ether complex; A2, after the reaction is completed, cooling the system to 40-50°C, adding phosphorus pentoxide in batches, and then stirring and refluxing at 95-105°C.

[0018] In this invention, the preparation process of allyl ether-modified epoxy phosphate surfactant is a multi-step organic synthesis reaction, the mechanism of which mainly involves the ring-opening reaction of epoxy groups and the phosphorylation reaction. In the first stage of the reaction, bisphenol A type epoxy resin serves as the main backbone, and the epoxy groups at both ends of its molecular chain have high reactivity. Under the action of Lewis acid catalyst boron trifluoride diethyl ether complex, the epoxy groups undergo a ring-opening reaction to form a carbocation intermediate. Subsequently, the epoxy groups in the allyl glycidyl ether molecule also undergo a similar ring-opening process. The allyl group in its molecular structure has good steric hindrance effect and reactivity, and can undergo a nucleophilic substitution reaction with the carbocation intermediate of epoxy resin to form an ether bond. The key to this stage is to control the reaction temperature and stirring time to ensure that the epoxy groups are fully ring-opened without cross-linking side reactions. During the reaction, the choice of solvent system is crucial. The mixed solvent of butyl acetate and n-butanol ensures the full dissolution of the reactants and controls the reaction rate by adjusting the polarity. In the second stage of the reaction, phosphorus pentoxide was added in batches after the reaction system was cooled to initiate a phosphorylation reaction. Phosphorus pentoxide, as a potent phosphorylating agent, first reacts with the secondary hydroxyl groups generated in the reaction system to form an intermediate phosphate ester compound. During this process, the phosphorus atoms in the phosphorus pentoxide molecule form coordinate bonds with the oxygen atoms of the hydroxyl groups, followed by a dehydration reaction to form phosphate ester bonds. Because phosphorus pentoxide has multiple reaction sites, the addition rate and temperature must be strictly controlled to avoid cross-linking or over-phosphorylation. After the reaction temperature is raised to an appropriate range, the remaining hydroxyl groups continue to react with the phosphate ester intermediate, ultimately forming an allyl ether-modified epoxy phosphate surfactant with a specific structure. Throughout the reaction, the introduction of the phosphate ester group significantly improves the surface activity and emulsifying properties of the product, while the retention of the allyl group provides reaction sites for potential subsequent functionalization modifications. The molecular structure of this surfactant simultaneously contains the rigid framework of an epoxy resin, the flexible segments of an allyl ether, and the hydrophilic groups of a phosphate ester; this unique structural design endows it with excellent emulsifying properties and interfacial activity. The epoxy framework provides rigid support, the allyl ether segments enhance molecular flexibility, and the phosphate ester groups endow the molecule with good water solubility and interfacial adsorption capabilities. This multifunctional molecular structure enables effective control of crystal growth direction during the subsequent preparation of copper sulfide, guiding the copper sulfide nanosheets to grow directionally along the three-dimensional structure of the butterfly wing template, thereby achieving precise control over their morphology.

[0019] According to a preferred embodiment of the present invention, in step A1, the temperature is raised to 58-62°C and the stirring time is 1-2 hours.

[0020] According to a preferred embodiment of the present invention, in step A2, the stirring and reflux reaction time is 3-4 hours.

[0021] According to a preferred embodiment of the present invention, the preparation method of the trisiloxane polyether phosphate surfactant includes: B1, under nitrogen protection, adding 1,1,1,3,5,5,5-heptamethyltrisiloxane and isopropanol to a high-pressure reactor, stirring to dissolve, and then adding an isopropanol solution of chloroplatinic acid; adding allyl polyether dropwise, and reacting at a temperature of 78-82°C; to obtain polyether-modified trisiloxane; B2, then transferring the polyether-modified trisiloxane to a three-necked flask, adding phosphorus pentoxide, and reacting under nitrogen protection at 89-91°C.

[0022] In this invention, the preparation of trisiloxane polyether phosphate surfactant is a typical process combining hydrosilylation and phosphorylation. In the first stage of the reaction, heptamethyltrisiloxane is used as the starting material, whose silane-hydrogen bonds in its molecular structure exhibit high reactivity. Under the catalysis of chloroplatinic acid, the silane-hydrogen bonds are activated to form a platinum-silicon complex intermediate. This complex intermediate coordinates with the carbon-carbon double bond in the allyl polyether molecule to form a transition state complex. Subsequently, a hydrosilylation reaction occurs, where silicon atoms form stable silicon-carbon bonds with the terminal carbon atoms, while hydrogen atoms in the silane-hydrogen bonds transfer to the intermediate carbon atoms, completing the entire addition process. The reaction needs to be carried out under an inert gas atmosphere to prevent catalyst deactivation and oxidation of the starting material. Temperature control is crucial; excessively high temperatures can lead to side reactions, while excessively low temperatures will slow down the reaction rate. After the hydrosilylation reaction is completed, a polyether-modified trisiloxane intermediate is obtained. This intermediate molecule has a unique structural feature of a trisiloxane hydrophobic head and a polyether hydrophilic tail, and has already exhibited certain surface activity. However, to further enhance its interfacial activity and functional properties, a second-stage phosphate esterification reaction is required. The intermediate is transferred to a reactor, and phosphorus pentoxide is added under strictly controlled conditions for phosphate esterification. Phosphorus pentoxide first reacts with the hydroxyl groups at the ends of the polyether chains to generate an acidic phosphate monoester intermediate. This reaction is a typical esterification process involving nucleophilic attack of phosphorus atoms on oxygen atoms and elimination of water molecules. Subsequently, under nitrogen protection and continuous stirring, the remaining hydroxyl groups continue to react with the phosphate ester intermediate to form the final trisiloxane polyether phosphate surfactant. The resulting surfactant molecule possesses a unique ternary structure: the trisiloxane head provides superior hydrophobicity and spreading ability, the polyether segments impart appropriate flexibility and water solubility, and the phosphate ester end groups enhance the molecule's interfacial activity and reactivity. This special structural design enables the surfactant to exhibit excellent surface tension reduction capabilities at both gas-liquid and liquid-liquid interfaces. In the preparation of copper sulfide, it can be effectively adsorbed at the crystal growth interface, preventing the aggregation of nanoparticles through steric hindrance and electrostatic repulsion, while guiding the crystals to grow along specific crystal planes, thereby achieving precise control over the microstructure of copper sulfide. Compared with other types of surfactants, this trisiloxane surfactant also has advantages such as good thermal stability and high biocompatibility, making it particularly suitable for high-temperature reaction conditions such as hydrothermal synthesis.

[0023] According to a preferred embodiment of the present invention, in step B1, the reaction time at 78-82°C is 4-6 hours.

[0024] According to a preferred embodiment of the present invention, in step B2, the reaction time under nitrogen protection at 89-91°C is 6-8 hours.

[0025] The present invention also provides a copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration, wherein the copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration is prepared according to the preparation method of the copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration.

[0026] The beneficial effects of this invention are as follows:

[0027] This invention provides a copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure and its preparation method, representing a significant technological advancement and excellent application effects. Firstly, by innovatively using two novel surfactants—allyl ether-modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant—precise control of the copper sulfide crystal growth process was successfully achieved. These two surfactants possess unique molecular structures and functional groups, enabling them to synergistically guide the directional growth of copper sulfide nanocrystals along the three-dimensional framework structure of the butterfly wing template, thereby perfectly replicating and preserving the butterfly wing's unique hierarchical porous structure and large specific surface area. Compared to traditional single surfactants, this composite surfactant system exhibits stronger morphology control and spatial guidance, overcoming problems such as morphological inhomogeneity and structural collapse present in conventional methods.

[0028] Secondly, the prepared copper sulfide material exhibits significant advantages in structural characteristics and performance. The material perfectly inherits the fine hierarchical structure of natural butterfly wings, forming a three-dimensional network of porous materials composed of interwoven two-dimensional nanosheets. This unique structure creates abundant active sites and efficient mass transfer channels. In photocatalytic applications, the material demonstrates excellent light absorption and charge separation efficiency, exhibiting extremely high degradation rates and complete mineralization capabilities for pollutants such as organic dyes. In the field of electrochemical energy storage, the material displays high specific capacity and excellent cycle stability, thanks to its unique hierarchical porous structure that provides ideal pathways for ion migration and electron transport, while effectively mitigating the volume expansion effect during charge and discharge.

[0029] Finally, the preparation process of this invention has significant technological advancements and application value. The entire preparation process is green and environmentally friendly, avoiding the use of toxic reagents, and both surfactants exhibit good biodegradability and environmental compatibility. The preparation method is simple to operate, with mild reaction conditions, suitable for large-scale production, and has significant economic benefits and industrialization prospects.

[0030] The obtained copper sulfide materials have shown broad application potential in multiple high-tech fields such as photocatalysis, energy storage, sensors, and environmental protection, providing new ideas and technical routes for the design and development of high-performance functional materials. Attached Figure Description

[0031] Appendix Figure 1This is a scanning electron microscope (SEM) image of the worm-like copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure in Example 1;

[0032] Appendix Figure 2 This is a scanning electron microscope (SEM) image of the nanoflower-like copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure in Example 2;

[0033] Appendix Figure 3 This is a scanning electron microscope (SEM) image of the natural butterfly wing three-dimensional hierarchical structure wrapped with a film of copper sulfide material in Example 3;

[0034] Appendix Figure 4 This is a scanning electron microscope (SEM) image of the sheet-like copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure in Example 4;

[0035] Appendix Figure 5 This is a scanning electron microscope (SEM) image of the nanosphere (~100 nm) copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure in Example 5;

[0036] Appendix Figure 6 This is a scanning electron microscope (SEM) image of the nanosphere (~50 nm) copper sulfide material with a natural butterfly wing three-dimensional hierarchical structure in Example 6. Detailed Implementation

[0037] The present application will now be described in further detail with reference to the accompanying drawings. It should be noted that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0038] The following is information on domestic suppliers of key related equipment and materials:

[0039] The heteromorphic purple-spotted butterfly was purchased from Shanghai Dieling Biotechnology Co., Ltd.

[0040] The thiourea was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0041] The ethanol was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0042] The deionized water was purchased from Hangzhou Wahaha Group Co., Ltd.

[0043] The four-necked flask was purchased from Shanghai Shenshun Biotechnology Co., Ltd.

[0044] The bisphenol A type epoxy resin was purchased from Sinopec Baling Petrochemical Co., Ltd.

[0045] The butyl acetate was purchased from Wuxi Yatai United Chemical Co., Ltd.

[0046] The n-butanol was purchased from Nanjing Chemical Reagent Co., Ltd.

[0047] The allyl glycidyl ether was purchased from Jiaxing Beihua Chemical Technology Co., Ltd.

[0048] The boron trifluoride diethyl ether complex was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0049] The phosphorus pentoxide was purchased from Tianjin Xiens Biochemical Technology Co., Ltd.

[0050] The nitrogen gas was purchased from Beijing Helium North Branch Gas Industry Co., Ltd.

[0051] The high-pressure reactor was purchased from Weihai Chemical Machinery Co., Ltd.

[0052] The 1,1,1,3,5,5,5-heptamethyltrisiloxane was purchased from Jinan World Chemical Co., Ltd.

[0053] The isopropanol was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0054] The chloroplatinic acid was purchased from Guizhou Platinum Industry Co., Ltd.

[0055] The allyl polyether was purchased from Jiangsu Chenhua New Materials Co., Ltd.

[0056] The three-necked flask was purchased from Shanghai Shenshun Biotechnology Co., Ltd.

[0057] The ethylenediaminetetraacetic acid was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0058] The Na2S solution was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0059] The K2S solution was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0060] The copper sulfate was purchased from Wuxi Yatai United Chemical Co., Ltd.

[0061] The copper chloride was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0062] The copper nitrate was purchased from Tianjin Xiens Biochemical Technology Co., Ltd.

[0063] The hexadecyltrimethylammonium bromide was purchased from Henan Juteng Chemical Products Co., Ltd.

[0064] Example 1

[0065] 25g of bisphenol A epoxy resin, 20g of butyl acetate, and 25g of n-butanol were added to a four-necked flask and heated to 60℃ and stirred for 1.5 hours. 15g of allyl glycidyl ether was added and reacted for 2 hours under the action of 2.5g of boron trifluoride diethyl ether complex. The system was cooled to 45℃, and 8g of phosphorus pentoxide was added in batches. Then, the mixture was stirred and refluxed at 100℃ for 3.5 hours to obtain an allyl ether modified epoxy phosphate surfactant. Separately, 20g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 50g of isopropanol were added to a high-pressure reactor and stirred to dissolve. Then, 0.1g of isopropanol solution of chloroplatinic acid was added. 30g of allyl polyether was added dropwise, and the mixture was reacted at 80°C for 5 hours to obtain polyether-modified trisiloxane. This was then transferred to a three-necked flask, 10g of phosphorus pentoxide was added, and the mixture was reacted at 90°C under nitrogen protection for 7 hours to obtain the trisiloxane polyether phosphate surfactant. 25g of butterfly wings were soaked in ethanol for 3 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 100g of 15% ethylenediaminetetraacetic acid solution and pretreated at 120℃ for 4 hours. After washing and drying with water, they were placed in 80g of 10% copper sulfate solution and soaked at 60℃ for 4 hours. After washing with ethanol, they were immersed in 50g of 0.8% sodium sulfide solution and reacted at room temperature for 2 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were put back into 100g of 10% copper sulfate solution, and 15g of thiourea, 1.0g of the allyl ether modified epoxy phosphate surfactant prepared above and 1.0g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 150℃ for 8 hours. After washing with deionized water and ethanol and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0066] Example 2

[0067] The preparation method is the same as in Example 1, except that 20g of bisphenol A epoxy resin, 18g of butyl acetate, and 20g of n-butanol are added to a four-necked flask, heated to 58°C and stirred for 2 hours; 12g of allyl glycidyl ether is added, and the mixture is reacted for 1.5 hours under the action of 2.0g of boron trifluoride diethyl ether complex; the system is cooled to 40°C, and 6g of phosphorus pentoxide is added in batches, then the mixture is stirred and refluxed at 95°C for 4 hours. Separately, 18g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 45g of isopropanol are added to a high-pressure reactor, stirred and dissolved, and then 0.08g of isopropanol solution of chloroplatinic acid is added; 25g of allyl polyether is added dropwise, and the mixture is reacted at 78°C for 6 hours to obtain polyether-modified trisiloxane; this is transferred to a three-necked flask, 8g of phosphorus pentoxide is added, and the mixture is reacted at 89°C under nitrogen protection for 8 hours. 20g of butterfly wings were soaked in ethanol for 2 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 80g of 10% ethylenediaminetetraacetic acid solution and pretreated at 100℃ for 5 hours. After washing and drying with water, they were placed in 70g of 8% copper chloride solution and soaked at 50℃ for 5 hours. After washing with ethanol, they were immersed in 40g of 0.5% potassium sulfide solution and reacted at room temperature for 1.5 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were placed back into 90g of 8% copper chloride solution, and 12g of thiourea, 0.8g of the allyl ether modified epoxy phosphate surfactant prepared above, and 0.9g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 130℃ for 10 hours. After washing with deionized water and ethanol, and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0068] Example 3

[0069] The preparation method is the same as in Example 1, except that 30g of bisphenol A epoxy resin, 22g of butyl acetate, and 30g of n-butanol are added to a four-necked flask, heated to 62°C and stirred for 1 hour; 18g of allyl glycidyl ether is added, and the mixture is reacted for 2.5 hours under the action of 3.0g of boron trifluoride diethyl ether complex; the system is cooled to 50°C, and 10g of phosphorus pentoxide is added in batches, then the mixture is stirred and refluxed at 105°C for 3 hours. Separately, 22g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 55g of isopropanol are added to a high-pressure reactor, stirred and dissolved, and then 0.12g of isopropanol solution of chloroplatinic acid is added; 35g of allyl polyether is added dropwise, and the mixture is reacted at 82°C for 4 hours to obtain polyether-modified trisiloxane; this is transferred to a three-necked flask, 12g of phosphorus pentoxide is added, and the mixture is reacted at 91°C under nitrogen protection for 6 hours. 30g of butterfly wings were soaked in ethanol for 4 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 120g of 20% ethylenediaminetetraacetic acid solution and pretreated at 140℃ for 3 hours. After washing and drying with water, they were placed in 90g of 12% copper nitrate solution and soaked at 70℃ for 3 hours. After washing with ethanol, they were immersed in 60g of 1.2% sodium sulfide solution and reacted at room temperature for 2.5 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were placed back into 110g of 12% copper nitrate solution, and 18g of thiourea, 1.2g of the allyl ether modified epoxy phosphate surfactant prepared above, and 1.1g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 170℃ for 6 hours. After washing with deionized water and ethanol, and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0070] Example 4

[0071] The preparation method is the same as in Example 1, except that 22g of bisphenol A epoxy resin, 19g of butyl acetate, and 22g of n-butanol are added to a four-necked flask and heated to 59°C and stirred for 1.2 hours; 14g of allyl glycidyl ether is added and reacted for 1.8 hours under the action of 2.2g of boron trifluoride diethyl ether complex; the system is cooled to 42°C, 7g of phosphorus pentoxide is added in batches, and then the mixture is stirred and refluxed at 98°C for 3.2 hours to obtain the allyl ether modified epoxy phosphate surfactant. Separately, 19 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 48 g of isopropanol were added to a high-pressure reactor and stirred to dissolve. Then, 0.09 g of isopropanol solution of chloroplatinic acid was added. 28 g of allyl polyether was added dropwise, and the reaction was carried out at 79 °C for 4.5 hours to obtain polyether-modified trisiloxane. This was then transferred to a three-necked flask, 9 g of phosphorus pentoxide was added, and the reaction was carried out at 89.5 °C under nitrogen protection for 7.5 hours to obtain trisiloxane polyether phosphate surfactant. 22g of butterfly wings were soaked in ethanol for 2.5 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 90g of 12% ethylenediaminetetraacetic acid solution and pretreated at 110℃ for 4.5 hours. After washing and drying with water, they were placed in 75g of 9% copper sulfate solution and soaked at 55℃ for 4.5 hours. After washing with ethanol, they were immersed in 45g of 0.7% sodium sulfide solution and reacted at room temperature for 1.8 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were placed back into 95g of 9% copper sulfate solution, and 16g of thiourea, 0.9g of the allyl ether modified epoxy phosphate surfactant prepared above, and 0.95g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 140℃ for 9 hours. After washing with deionized water and ethanol, and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0072] Example 5

[0073] The preparation method is the same as in Example 1, except that 28g of bisphenol A epoxy resin, 21g of butyl acetate, and 28g of n-butanol are added to a four-necked flask and heated to 61°C and stirred for 1.8 hours; 16g of allyl glycidyl ether is added and reacted for 2.2 hours under the action of 2.8g of boron trifluoride diethyl ether complex; the system is cooled to 48°C, and 9g of phosphorus pentoxide is added in batches, and then stirred and refluxed at 102°C for 3.8 hours to obtain allyl ether modified epoxy phosphate surfactant. Separately, 21 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 52 g of isopropanol were added to a high-pressure reactor and stirred to dissolve. Then, 0.11 g of isopropanol solution of chloroplatinic acid was added. 32 g of allyl polyether was added dropwise, and the reaction was carried out at 81 °C for 5.5 hours to obtain polyether-modified trisiloxane. This was then transferred to a three-necked flask, 11 g of phosphorus pentoxide was added, and the reaction was carried out at 90.5 °C under nitrogen protection for 6.5 hours to obtain trisiloxane polyether phosphate surfactant. 28g of butterfly wings were soaked in ethanol for 3.5 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 110g of 18% ethylenediaminetetraacetic acid solution and pretreated at 130℃ for 3.5 hours. After washing and drying with water, they were placed in 85g of 11% copper chloride solution and soaked at 65℃ for 3.5 hours. After washing with ethanol, they were immersed in 55g of 1.0% potassium sulfide solution and reacted at room temperature for 2.2 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were placed back into 105g of 11% copper chloride solution, and 17g of thiourea, 1.1g of the allyl ether modified epoxy phosphate surfactant prepared above, and 1.05g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 160℃ for 7 hours. After washing with deionized water and ethanol, and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0074] Example 6

[0075] The preparation method is the same as in Example 1, except that 24g of bisphenol A epoxy resin, 20.5g of butyl acetate, and 26g of n-butanol are added to a four-necked flask and heated to 60.5°C and stirred for 1.6 hours; 15.5g of allyl glycidyl ether is added and reacted for 2.1 hours under the action of 2.6g of boron trifluoride diethyl ether complex; the system is cooled to 46°C, and 8.5g of phosphorus pentoxide is added in batches, and then the mixture is stirred and refluxed at 103°C for 3.3 hours to obtain the allyl ether modified epoxy phosphate surfactant. Separately, 20.5 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 53 g of isopropanol were added to a high-pressure reactor and stirred to dissolve. Then, 0.105 g of isopropanol solution of chloroplatinic acid was added. 33 g of allyl polyether was added dropwise, and the reaction was carried out at 80.5 °C for 4.8 hours to obtain polyether-modified trisiloxane. This was then transferred to a three-necked flask, and 10.5 g of phosphorus pentoxide was added. The reaction was carried out at 90.2 °C under nitrogen protection for 7.2 hours to obtain trisiloxane polyether phosphate surfactant. 26g of butterfly wings were soaked in ethanol for 3.2 hours, then washed with distilled water and dried in air. The dried butterfly wings were placed in 115g of 16% ethylenediaminetetraacetic acid solution and pretreated at 125℃ for 4.2 hours. After washing and drying with water, they were placed in 87g of 10.5% copper nitrate solution and soaked at 62℃ for 4.2 hours. After washing with ethanol, they were immersed in 58g of 0.9% sodium sulfide solution and reacted at room temperature for 2.3 hours to form CuS seed crystals. The butterfly wings loaded with seed crystals were placed back into 108g of 10.5% copper nitrate solution, and 16.5g of thiourea, 1.15g of the allyl ether modified epoxy phosphate surfactant prepared above, and 1.08g of trisiloxane polyether phosphate surfactant were added. The mixture was transferred to an autoclave and reacted at 155℃ for 8.5 hours. After washing with deionized water and ethanol, and drying in air, copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings was obtained.

[0076] The preparation method is the same as in Example 1, except that no surfactant is added.

[0077] Comparative Example 2

[0078] The preparation method is the same as in Example 1, except that only allyl ether modified epoxy phosphate surfactant is added.

[0079] Comparative Example 3

[0080] The preparation method is the same as in Example 1, except that hexadecyltrimethylammonium bromide is used instead of the two specially made surfactants.

[0081] II. Performance Testing and Result Analysis

[0082] The performance of copper sulfide with a three-dimensional hierarchical structure of natural butterfly wings prepared in Examples 1-3 and Comparative Examples 1-3 was tested using the following methods:

[0083] The microstructure of the material was observed using a Hitachi SU8010 field emission scanning electron microscope (SEM) with an accelerating voltage of 15 kV and a working distance of 8 mm. Samples were vacuum-plated with gold for 60 s before testing. Specific surface area and pore structure were measured using a Micron Instruments ASAP 2020 fully automated specific surface area and porosity analyzer. Samples were degassed under vacuum at 150 °C for 6 h, and N2 adsorption-desorption isotherms were measured at 77 K liquid nitrogen. Specific surface area was calculated using the BET method, and pore size distribution was calculated from the desorption branch using the BJH model. Crystal structure was analyzed using a Rigaku D / max-2500 X-ray diffractometer (RTD) with a Cu target Kα radiation source (λ = 0.15418 nm), a tube voltage of 40 kV, a tube current of 100 mA, a scanning range of 10–80° (2θ), and a scanning speed of 5° / min. Photocatalytic performance test: 200 mL of methylene blue solution with a concentration of 20 mg / L was prepared, and 0.1 g of catalyst was added. After magnetic stirring in the dark for 30 min to reach adsorption equilibrium, photocatalytic degradation was carried out under irradiation of a 300 W xenon lamp (Beijing Zhongjiao Jinyuan CEL-HXF300). 4 mL of sample was taken every 20 min, filtered through a 0.22 μm microporous membrane, and the absorbance was measured at 664 nm using a Beijing Purkinje TU-1901 UV-Vis spectrophotometer. The degradation rate was calculated using the formula η = (1 - C / C0) × 100%, where C0 is the initial concentration and C is the concentration after the reaction. Electrochemical performance was tested using a Shanghai Chenhua CHI660E electrochemical workstation. A three-electrode system was used: the working electrode was prepared by mixing and grinding copper sulfide, acetylene black, and polyvinylidene fluoride (PVDF) with a natural butterfly wing three-dimensional hierarchical structure (prepared in Examples 1-3 and Comparative Examples 1-3) in a mass ratio of 8:1:1, coating it onto a 1cm × 1cm nickel foam (approximately 2mg loading), and pressing it into a sheet under 10MPa pressure; the counter electrode was a platinum sheet electrode (1cm × 1cm); the reference electrode was a saturated calomel electrode (SCE); and the electrolyte was a 1mol / L Na₂SO₄ solution. Cyclic voltammetry was performed with a scan rate of 5-100mV / s and a potential window of -0.2-0.8V; constant current charge-discharge testing was performed with a current density of 1-10A / g and a potential window of -0.2-0.8V; the specific capacitance was calculated using the formula C = IΔt / (mΔV), where I is the discharge current (A), Δt is the discharge time (s), m is the mass of the active material (g), and ΔV is the potential window (V). Cyclic stability testing was performed at a current density of 5 A / g for 5000 charge-discharge cycles.

[0084] Table 1: Performance test results of each embodiment and comparative example

[0085]

[0086] As shown in Table 1, the test results fully demonstrate that Examples 1-3 of this invention effectively solve the four major technical problems existing in current copper sulfide materials by innovatively using the synergistic combination of allyl ether-modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant. Firstly, in terms of specific surface area, Example 1 reaches 285 m² / g, an increase of over 110% compared to Comparative Example 1's 135 m² / g. This is due to the two surfactants precisely guiding the copper sulfide to grow epitaxially along the three-dimensional skeleton of the butterfly wing, perfectly replicating its hierarchical pore structure, while the comparative material suffers structural collapse due to a lack of effective morphology control. Regarding active sites, Example 1 achieves a photocatalytic degradation rate as high as 98.5%, far superior to Comparative Example 1's 65.3%. This is because the specially formulated surfactant enables the material to form abundant mesoporous and macroporous structures, providing ample channels and active centers for reactant transport and surface reactions.

[0087] Regarding the precision of morphology control, the materials in the examples exhibited a highly consistent hierarchical structure, while Comparative Example 2, using only a single surfactant, showed a photocatalytic degradation rate reduced to 82.4%, demonstrating the indispensable synergistic effect of the two surfactants: the allyl ether-modified epoxy phosphate surfactant controls the crystal growth direction by specifically binding its phosphate groups to the crystal surface; the trisiloxane polyether phosphate surfactant reduces interfacial energy through its unique trisiloxane structure, guiding the orderly self-assembly of nanosheets. This dual regulatory mechanism ensures that the fine structure of the butterfly wing template is not destroyed during replication.

[0088] Regarding structural stability, Example 1 retained 92.3% of its capacity after 5000 charge-discharge cycles, while Comparative Example 3, using the conventional surfactant cetyltrimethylammonium bromide, showed a stability decrease to 80.3%. This is because the specially formulated surfactant forms a stable bond with the copper sulfide crystals through strong chemical bonding, effectively buffering volume changes during charge-discharge and preventing structural collapse. Furthermore, the uniform pore size distribution and good mechanical strength of the materials in these examples further ensured long-term cycle stability.

[0089] In summary, this invention, through the synergistic effect of two specially formulated surfactants, successfully achieves precise control of the multi-level structure of copper sulfide materials from the nanometer to the micrometer scale. It completely solves the technical problem that traditional methods cannot simultaneously achieve high specific surface area, abundant active sites, precise morphology control, and long-term stability, providing a brand-new solution for the controllable preparation of high-performance copper sulfide materials.

[0090] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A process for the preparation of copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration, characterized by the steps of The preparation method of the copper sulfide with natural butterfly wing three-dimensional hierarchical configuration comprises the following steps: S1, soaking the butterfly wing in an ethanol solution at room temperature, then washing with distilled water, and drying in air; placing the dried butterfly wing in an ethylenediaminetetraacetic acid solution and pretreating at 80-150 DEG C; S2, then washing with a solvent and drying; placing the pretreated butterfly wing in a copper ion solution, soaking at 30-80 DEG C, and then washing with ethanol; immersing the butterfly wing loaded with copper ions in a sulfur ion solution at room temperature to form CuS crystal seeds; S3, re-placing the butterfly wing loaded with CuS crystal seeds in a copper ion solution, adding thiourea, allyl ether modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant, and transferring the reaction system to an autoclave for constant temperature reaction at 100-180 DEG C; The preparation method of the allyl ether modified epoxy phosphate surfactant comprises the following steps: A1, adding bisphenol A type epoxy resin, butyl acetate and n-butanol in a four-necked flask, and stirring at a temperature of 58-62 DEG C; adding allyl glycidyl ether and reacting under the action of boron trifluoride ether complex; A2, after the reaction is completed, cooling the system to 40-50 DEG C, adding phosphorus pentoxide in batches, and then stirring and refluxing at 95-105 DEG C. The preparation method of the trisiloxane polyether phosphate surfactant comprises the following steps: B1, under nitrogen protection, adding 1,1,1,3,5,5,5-heptamethyltrisiloxane and isopropanol in a high-pressure reaction kettle, stirring and dissolving, and then adding chloroplatinic acid isopropanol solution; adding allyl polyether dropwise and reacting at a temperature of 78-82 DEG C; obtaining polyether modified trisiloxane; B2, then transferring the polyether modified trisiloxane to a three-necked flask, adding phosphorus pentoxide, and reacting under nitrogen protection at 89-91 DEG C.

2. The method for preparing copper sulfide having a natural butterfly wing three-dimensional hierarchical configuration according to claim 1, characterized in that, In step S1, the pretreatment time at 80-150 DEG C is 2-6 h.

3. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, In step S2, the soaking time at 30-80 DEG C is 2-6 h.

4. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, In step A1, the stirring time at a temperature of 58-62 DEG C is 1-2 h.

5. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, In step A2, the stirring and refluxing reaction time is 3-4 h.

6. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, In step B1, the reaction time at a temperature of 78-82 DEG C is 4-6 h.

7. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, In step B2, the reaction time under nitrogen protection at a temperature of 89-91 DEG C is 6-8 h.

8. A copper sulfide having a native butterfly wing three-dimensional hierarchical configuration, characterized in that, The copper sulfide with natural butterfly wing three-dimensional hierarchical configuration is prepared by the preparation method of the copper sulfide with natural butterfly wing three-dimensional hierarchical configuration according to any one of claims 1-7.

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