Copper sulfide with natural butterfly wing three-dimensional hierarchical configuration and preparation method thereof

Abstract

The invention discloses copper sulfide with a natural butterfly wing three-dimensional hierarchical configuration and a preparation method thereof, and belongs to the technical field of nano materials, the material is prepared by taking a butterfly wing as a biological template, sequentially performing copper ion soaking and sulfur ion treatment after pretreatment activation to form a seed crystal, and finally performing hydrothermal reaction under the induction of a surfactant. Wherein two special surfactants are adopted, namely an allyl ether modified epoxy phosphate surfactant is prepared through epoxy ring opening and phosphoric acid esterification reaction, and a trisiloxane polyether phosphate surfactant is prepared through hydrosilylation and phosphoric acid esterification reaction. The unique three-dimensional hierarchical porous structure of the butterfly wing is successfully copied, the obtained copper sulfide material has high specific surface area and rich active sites and shows excellent performance in the fields of photocatalytic degradation, electrochemical energy storage and the like, and the preparation process is green and economical and suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanomaterials, and particularly relates to a copper sulfide with a natural butterfly wing three-dimensional hierarchical structure and a preparation method thereof. BACKGROUND

[0002] As an important p-type semiconductor material, copper sulfide has broad application prospects in the fields of photoelectric conversion, catalytic degradation and energy storage. Traditional preparation methods of copper sulfide such as hydrothermal method, hot injection method and ordinary template method can prepare copper sulfide materials with different morphologies, but they generally have problems such as insufficient control precision of morphology, poor structural stability, complex process, and use of toxic reagents. In particular, the specific surface area of the copper sulfide material prepared by the conventional method is limited, the active sites are insufficient, and the material is prone to agglomeration, which seriously affects the performance of the material in the application of photocatalysis and electrochemistry. In addition, the existing method still has great limitations in precisely controlling the microstructure of the material, and it is difficult to realize the controllable preparation of multi-level pore structure, which greatly limits the performance of copper sulfide material in practical application.

[0003] In recent years, the biological template method as a new material preparation method has attracted widespread attention. This method uses the fine biological structure formed by long-term evolution in nature as a template to prepare functional materials with multi-level ordered structure. Butterfly wings, as a typical biological template, have a unique three-dimensional hierarchical porous structure, high specific surface area and good mechanical stability, providing an ideal microstructure skeleton for functional materials. However, direct use of butterfly wing templates has problems such as insufficient active sites, high surface energy and easy agglomeration, and weak binding force with inorganic materials. Although there are reports in the prior art on the use of butterfly wing templates to prepare functional materials, there are still obvious deficiencies in the selection and use of surfactants. Commonly used commercial surfactants such as hexadecyl trimethyl ammonium bromide and sodium dodecyl sulfate have limited functions and control precision, and cannot realize precise control of the morphology of the material, making it difficult to fully utilize the structural advantages of the butterfly wing template.

[0004] In view of the deficiencies of the prior art, it is urgent to develop a new surfactant system and a perfect preparation process to fully utilize the unique structural advantages of the butterfly wing template and prepare copper sulfide materials with precisely controlled three-dimensional hierarchical structure. The present application successfully solves the problem of single function and insufficient control precision of surfactants in the prior art by innovatively developing two new surfactants, allyl ether modified epoxy phosphate surfactant and trisiloxane polyether phosphate surfactant. The two surfactants can work together to precisely guide the growth of copper sulfide crystals at the molecular level, while ensuring the green environmental protection and economic feasibility of the preparation process, providing a new technical route for preparing high-performance copper sulfide materials. SUMMARY

[0005] The application aims to provide a copper sulfide with a natural butterfly wing three-dimensional hierarchical configuration and a preparation method thereof, 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 application achieves the above-mentioned purpose by the following technical scheme: A preparation method of copper sulfide with a natural butterfly wing three-dimensional hierarchical configuration, steps comprising: S1, soaking the butterfly wing in an ethanol solution at room temperature, then cleaning 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 cleaning and drying with a solvent; placing the pretreated butterfly wing in a copper ion solution, soaking at 30-80 DEG C, then cleaning with ethanol; immersing the butterfly wing loaded with copper ions in a sulfur ion solution at room temperature to form CuS crystal seeds; S3, 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, transferring the reaction system to an autoclave and reacting at 100-180 DEG C.

[0007] According to the preferred embodiment of the application, the butterfly wing template is a butterfly wing with clear, complete and regular three-dimensional hierarchical micro-nano structure.

[0008] According to the preferred embodiment of the application, the copper source is at least one selected from copper sulfate, copper chloride and copper nitrate.

[0009] According to the preferred embodiment of the application, the sulfur ion solution is Na2S or K2S solution.

[0010] In the present application, the preparation of copper sulfide with natural butterfly wing three-dimensional hierarchical configuration is a process based on biomimetic template method and surfactant-induced crystal growth, and the reaction mechanism involves multiple stages of chemical action and physical process. First, the butterfly wing template is activated by a pretreatment process, and the carboxyl functional groups in the ethylenediaminetetraacetic acid solution form coordinate bonds with the biomolecules on the surface of the butterfly wing, while removing the impurities and lipids on the surface and exposing more active sites. This pretreatment process greatly enhances the surface activity and adsorption capacity of the butterfly wing template, providing a good foundation for subsequent metal ion adsorption. The temperature treatment helps the ethylenediaminetetraacetic acid molecules to better penetrate into the multi-level pore structure of the butterfly wing and form stable complexes with the chitin and other biological macromolecules therein, thereby achieving effective modification of the template surface. In the seed formation stage, the pretreated butterfly wing template is immersed in a copper ion solution, and the copper ions in the solution are adsorbed on the active sites on the surface of the butterfly wing 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 micro- and nano-level multi-level pore structure ensures the uniform distribution of copper ions. Subsequently, when immersed in a sulfur ion solution, the adsorbed copper ions react with the sulfur ions to form copper sulfide nuclei on the surface of the butterfly wing. These nuclei, as seeds for subsequent crystal growth, directly determine the morphology of the final product in terms of their distribution density and uniformity. The room temperature reaction conditions help to control the formation rate of the nuclei, avoiding the agglomeration or uneven distribution of the nuclei caused by too fast reaction. The final hydrothermal reaction stage is a key step in the entire preparation process. The butterfly wing loaded with seeds is reinserted into the reaction system, and thiourea is added as a sulfur source, along with two specially designed surfactants. Under hydrothermal conditions, thiourea gradually decomposes to release sulfur ions, which react with copper ions in the solution to form copper sulfide. The two surfactants work together, with the allyl ether-modified epoxy phosphate surfactant controlling the growth direction of the crystal through its phosphate groups, and the trisiloxane polyether phosphate surfactant reducing the interfacial tension and guiding the crystal to grow along the three-dimensional structure of the butterfly wing template. The high-temperature and high-pressure hydrothermal environment promotes the oriented growth and self-assembly of the copper sulfide crystals, ultimately forming copper sulfide materials that perfectly replicate the three-dimensional hierarchical structure of the butterfly wing template. This special structure not only maintains the fine morphological features of the butterfly wing template, but also endows the material with excellent physical and chemical properties, laying a foundation for its application in the fields of photocatalysis and energy storage. The entire preparation process embodies the perfect combination of biomimetic template method and surfactant-induced crystal growth, and exhibits good controllability and repeatability.

[0011] According to the preferred embodiment of the present application, in step S1, the pretreatment time at 80-150°C is 2-6h.

[0012] According to the preferred embodiment of the present application, in step S2, the soaking time at 30-80°C is 2-6h.

[0013] According to the preferred embodiment of the present application, the preparation method of the allyl ether modified epoxy phosphate surfactant comprises: A1, adding bisphenol A type epoxy resin, butyl acetate and n-butanol in a four-necked flask, and stirring at 58-62°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°C, adding phosphorus pentoxide in batches, and then stirring and refluxing at 95-105°C.

[0014] In the present application, the preparation process of allyl ether modified epoxy phosphate surfactant is a multi-step organic synthesis reaction, and the mechanism mainly involves ring-opening reaction of epoxy group and phosphate esterification reaction. In the first stage reaction, bisphenol A type epoxy resin is used as the main skeleton, and the epoxy groups at both ends of the molecular chain have high reactivity. Under the action of Lewis acid catalyst boron trifluoride ether complex, the epoxy group undergoes ring-opening reaction to form a carbocation intermediate. Subsequently, the epoxy group in the allyl glycidyl ether molecule also undergoes a similar ring-opening process, and the allyl group in the molecular structure has good steric hindrance effect and reactivity, which can undergo nucleophilic substitution reaction with the carbocation intermediate of the epoxy resin to form ether bond connection. The key of this stage is to control the reaction temperature and stirring time to ensure that the epoxy group is fully ring-opened without crosslinking side reaction. During the reaction process, the selection of the solvent system is crucial, and the mixed solvent of butyl acetate and n-butanol can ensure the sufficient dissolution of the reactants and control the reaction rate by adjusting the polarity. In the second stage reaction, the reaction system is cooled and phosphorus pentoxide is added in batches for phosphate esterification reaction. As a strong phosphorylating agent, phosphorus pentoxide first reacts with the secondary hydroxyl group generated in the reaction system to form a phosphate intermediate. In this process, the phosphorus atom in the phosphorus pentoxide molecule forms a coordination bond with the hydroxyl oxygen atom, and then undergoes dehydration reaction to form a phosphate ester bond. Since phosphorus pentoxide has multiple reaction sites, the addition speed and temperature need to be strictly controlled to avoid crosslinking or excessive phosphorylation. After the reaction temperature is increased to an appropriate range, the remaining hydroxyl group continues to react with the phosphate intermediate to finally form an allyl ether modified epoxy phosphate surfactant with a specific structure. During the entire reaction process, the introduction of phosphate groups greatly improves the surface activity and emulsifying performance of the product, and the retention of allyl group provides a reaction site for subsequent functional modification. The molecular structure of the surfactant contains the rigid skeleton of epoxy resin, the flexible segment of allyl ether and the hydrophilic group of phosphate, and this special structure design makes it have excellent emulsifying performance and interfacial activity. The epoxy skeleton provides rigid support, the allyl ether segment enhances the flexibility of the molecule, and the phosphate group endows the molecule with good water solubility and interfacial adsorption capacity. This multifunctional molecular structure enables it to effectively control the crystal growth direction during the subsequent preparation of copper sulfide, guiding the directional growth of copper sulfide nanosheets along the three-dimensional structure of butterfly wing template, thereby realizing precise control of the morphology.

[0015] According to the preferred embodiment of the present application, in step A1, the stirring time at 58-62°C is 1-2h.

[0016] According to the preferred embodiment of the present application, in step A2, the stirring reflux reaction time is 3-4h.

[0017] According to the preferred embodiment of the present application, the preparation method of the trisiloxane polyether phosphate surfactant comprises: B1, under the protection of nitrogen, 1,1,1,3,5,5,5-heptamethyltrisiloxane and isopropanol are added into a high-pressure reaction kettle, and after stirring and dissolving, an isopropanol solution of chloroplatinic acid is added; allyl polyether is added dropwise, and reaction is carried out at a temperature of 78-82℃; polyether modified trisiloxane is obtained; B2, then the polyether modified trisiloxane is transferred to a three-necked flask, and phosphorus pentoxide is added, and reaction is carried out under the protection of nitrogen at 89-91℃.

[0018] In the present invention, the preparation of trisiloxane polyether phosphate surfactant is a typical process of combination of hydrosilylation and phosphonation. In the first stage reaction, heptamethyltrisiloxane is used as the starting material. The Si-H bond in the molecule has high reactivity. Under the catalysis of chloroplatinic acid, the Si-H bond is 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. Then the hydrosilylation reaction occurs, and the silicon atom forms a stable Si-C bond with the terminal carbon atom, while the hydrogen atom in the Si-H bond is transferred to the intermediate carbon atom, completing the entire addition process. The reaction needs to be carried out under inert gas protection to prevent the catalyst from being deactivated and the raw materials from being oxidized. Temperature control is crucial, as too high a temperature will cause side reactions, while too low a temperature will slow down the reaction rate. After the completion of the hydrosilylation reaction, the polyether-modified trisiloxane intermediate is obtained. This intermediate molecule has a unique structure of trisiloxane hydrophobic head and polyether hydrophilic tail, and has shown certain surface activity. However, in order to further enhance its interfacial activity and functional properties, a second stage of phosphonation reaction is needed. The intermediate is transferred to the reactor, and phosphorus pentoxide is added under strict control conditions for phosphonation. Phosphorus pentoxide first reacts with the hydroxyl group at the end of the polyether chain to form an acidic phosphoric monoester intermediate. This reaction is a typical esterification process involving nucleophilic attack of phosphorus and oxygen atoms and elimination of water molecules. Then, under the protection of nitrogen and continuous stirring, the remaining hydroxyl groups continue to react with the phosphoric acid ester intermediate to form the final trisiloxane polyether phosphate surfactant. The final surfactant molecule has a unique ternary structure: the trisiloxane head provides super strong hydrophobicity and spreading ability, the polyether segment gives the molecule appropriate flexibility and water solubility, and the phosphate end group enhances the interfacial activity and reactivity of the molecule. This special structure design enables the surfactant to exhibit excellent surface tension reduction ability at both gas-liquid and liquid-liquid interfaces. In the preparation of copper sulfide, it can effectively adsorb on the crystal growth interface, prevent the agglomeration of nanoparticles through steric hindrance and electrostatic repulsion, and guide the crystal to grow along a specific crystal face direction, thereby achieving precise control of the micro-morphology of copper sulfide. Compared with other types of surfactants, this trisiloxane-based surfactant also has the advantages of good thermal stability, biocompatibility, etc., and is particularly suitable for high-temperature reaction conditions such as hydrothermal synthesis.

[0019] According to the preferred embodiment of the present invention, in step B1, the reaction time at 78-82℃ is 4-6h.

[0020] According to the preferred embodiment of the present invention, in step B2, the reaction time under nitrogen protection at 89-91℃ is 6-8h.

[0021] The application also provides the copper sulfide with the natural butterfly wing three-dimensional hierarchical configuration, which is prepared according to the preparation method of the copper sulfide with the natural butterfly wing three-dimensional hierarchical configuration.

[0022] The application has the following beneficial effects: The application provides the copper sulfide with the natural butterfly wing three-dimensional hierarchical configuration and a preparation method thereof, which has significant technical progress and excellent application effects. First, by innovatively using two new surfactants, an allyl ether modified epoxy phosphate surfactant and a trisiloxane polyether phosphate surfactant, the growth process of the copper sulfide crystal is successfully controlled. The two surfactants have unique molecular structures and functional groups, can synergistically act in the synthesis process, effectively guide the directional growth of the copper sulfide nanocrystal along the three-dimensional skeleton structure of the butterfly wing template, and thus perfectly copy and retain the unique multi-level channel structure and large specific surface area of the butterfly wing. Compared with the traditional single surfactant, the composite surfactant system exhibits stronger morphology control ability and spatial orientation effect, and overcomes the problems of uneven morphology and structure collapse in the conventional method.

[0023] Second, the prepared copper sulfide material has outstanding advantages in structural characteristics and performance. The material perfectly inherits the fine hierarchical structure of the natural butterfly wing, forms a three-dimensional network porous material composed of two-dimensional nanosheets staggered assembly, and such a unique structure creates rich active sites and efficient mass transfer channels. In the photocatalytic application, the material exhibits excellent light absorption capacity and charge separation efficiency, and has a very high degradation rate and complete mineralization capacity for pollutants such as organic dyes. In the field of electrochemical energy storage, the material exhibits high specific capacity and excellent cycle stability, which is due to the unique multi-level channel structure providing an ideal path for ion migration and electron transport, and effectively relieving the volume expansion effect in the charging and discharging process.

[0024] Finally, the preparation process of the application has obvious technical progress and application value. The whole preparation process is green and environmentally friendly, avoiding the use of toxic reagents, and the two surfactants have good biodegradability and environmental compatibility. The preparation method is simple to operate, the reaction conditions are mild, and is suitable for large-scale production, which has significant economic benefits and industrialization prospects.

[0025] The obtained copper sulfide material exhibits broad application potential in multiple high-tech fields such as photocatalysis, energy storage, sensors, environmental protection, and provides a new idea and technical route for the design and development of high-performance functional materials. BRIEF DESCRIPTION OF DRAWINGS

[0026] ATTACHMENT Figure 1is a scanning electron microscope (SEM) image of the worm-like cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration in Example 1; attached Figure 2 is a scanning electron microscope (SEM) image of the nanoflower-like cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration in Example 2; attached Figure 3 is a scanning electron microscope (SEM) image of the film-like cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration wrapped in a layer in Example 3; attached Figure 4 is a scanning electron microscope (SEM) image of the sheet-like cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration in Example 4; attached Figure 5 is a scanning electron microscope (SEM) image of the nanospherical (~100 nm) cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration in Example 5; attached Figure 6 is a scanning electron microscope (SEM) image of the nanospherical (~50 nm) cupric sulfide material with natural butterfly wing three-dimensional hierarchical configuration in Example 6. DETAILED DESCRIPTION

[0027] The application will be further described in details below with reference to the accompanying drawings. It is necessary to point out here that the following detailed description is only used to further illustrate the application and cannot be understood as limiting the scope of protection of the application. Those skilled in the art can make some non-essential improvements and adjustments to the application according to the above application content.

[0028] The main related equipment and material suppliers in China are as follows: The abnormal purple butterfly was purchased from Shanghai Butterfly Ling Biological Technology Co., Ltd.

[0029] The thiourea was purchased from China Reagent Co., Ltd.

[0030] The ethanol was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0031] The deionized water was purchased from Hangzhou Wahaha Group Co., Ltd.

[0032] The four-necked flask was purchased from Shanghai Shenshun Biological Technology Co., Ltd.

[0033] The bisphenol A type epoxy resin was purchased from SINOPEC Baling Petrochemical Co., Ltd.

[0034] The butyl acetate was purchased from Wuxi Yatai United Chemical Co., Ltd.

[0035] The n-butanol was purchased from Nanjing Chemical Reagent Co., Ltd.

[0036] The allyl glycidyl ether was purchased from Jiaxing Beihua Chemical Technology Co., Ltd.

[0037] The boron trifluoride ether complex was purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0038] The diphosphorus pentoxide was purchased from Tianjin Xinsiyuan Biochemical Technology Co., Ltd.

[0039] The nitrogen was purchased from Beijing Helunbei Gas Industry Co., Ltd.

[0040] The high-pressure reaction kettle was purchased from Weihai Chemical Machinery Co., Ltd.

[0041] The 1,1,1,3,5,5,5-heptamethyltrisiloxane was purchased from Jinan Wolde Chemical Co., Ltd.

[0042] The isopropanol was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0043] The chloroplatinic acid was purchased from Guiyan Platinum Industry Co., Ltd.

[0044] The allyl polyether was purchased from Jiangsu Chenhua New Material Co., Ltd.

[0045] The three-necked flask was purchased from Shanghai Shenshun Biological Technology Co., Ltd.

[0046] The ethylenediamine tetraacetic acid was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0047] The Na2S solution was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0048] The K2S solution was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0049] The copper sulfate was purchased from Wuxi Yatai United Chemical Co., Ltd.

[0050] The copper chloride was purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0051] The copper nitrate was purchased from Tianjin Xinsiyuan Biochemical Technology Co., Ltd.

[0052] The cetyltrimethylammonium bromide was purchased from Henan Juteng Chemical Product Co., Ltd.

[0053] Example 1

[0054] Take bisphenol A type epoxy resin 25 g, butyl acetate 20 g, n-butanol 25 g into four-necked flask, heated to 60 °C stirring 1.5 hours; add allyl glycidyl ether 15 g, under the action of boron trifluoride etherate 2.5 g reaction 2 hours; the system is cooled to 45 °C, batch adding phosphorus pentoxide 8 g, then stirring at 100 °C reflux reaction 3.5 hours, prepared allyl ether modified epoxy phosphate surfactant. Take 1,1,1,3,5,5,5-heptamethyltrisiloxane 20 g and isopropanol 50 g into high pressure reactor, stirring after adding chloroplatinic acid isopropanol solution 0.1 g; drop allyl polyether 30 g, at 80 °C for 5 hours; get polyether modified trisiloxane; it is transferred to three-necked flask, adding phosphorus pentoxide 10 g, at 90 °C nitrogen protection reaction 7 hours, prepared trisiloxane polyether phosphate surfactant. Take butterfly wings 25 g soaked in ethanol for 3 hours, then washed with distilled water, dried in air; the dried butterfly wings is placed in 15% concentration of ethylenediaminetetraacetic acid solution 100 g, pretreatment at 120 °C for 4 hours; washed with water and dried, then placed in 10% copper sulfate solution 80 g, soaked at 60 °C for 4 hours; washed with ethanol, then immersed in 0.8% sodium sulfide solution 50 g, room temperature reaction 2 hours to form CuS seed; the butterfly wings loaded with seed is placed in 10% copper sulfate solution 100 g, adding thiourea 15 g, the above prepared allyl ether modified epoxy phosphate surfactant 1.0 g and trisiloxane polyether phosphate surfactant 1.0 g, transferred to autoclave at 150 °C for 8 hours, then washed with deionized water, ethanol, dried in air to prepare copper sulfide with natural butterfly three-dimensional hierarchical configuration.

[0055] Example 2 The preparation method is the same as that of Example 1, except that 20 g of bisphenol A type epoxy resin, 18 g of butyl acetate and 20 g of n-butanol are added into a four-necked flask, and the temperature is raised to 58°C for stirring for 2 hours; 12 g of allyl glycidyl ether is added, and the reaction is carried out for 1.5 hours under the action of 2.0 g of boron trifluoride etherate; the system is cooled to 40°C, 6 g of phosphorus pentoxide is added in batches, and then the reaction is carried out for 4 hours under stirring and reflux at 95°C. 18 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 45 g of isopropyl alcohol are added into a high-pressure reaction kettle, 0.08 g of chloroplatinic acid isopropanol solution is added after stirring and dissolving, 25 g of allyl polyether is added dropwise, and the reaction is carried out for 6 hours at 78°C; polyether-modified trisiloxane is obtained; it is transferred into a three-necked flask, 8 g of phosphorus pentoxide is added, and the reaction is carried out for 8 hours under nitrogen protection at 89°C. 20 g of butterfly wings are soaked in ethanol for 2 hours, washed with distilled water, and dried in air; the dried butterfly wings are placed in 80 g of 10% ethylenediaminetetraacetic acid solution, pretreated at 100°C for 5 hours, washed and dried with water, placed in 70 g of 8% copper chloride solution, soaked at 50°C for 5 hours, washed with ethanol, then immersed in 40 g of 0.5% potassium sulfide solution for reaction at room temperature for 1.5 hours to form CuS crystal seeds; the butterfly wings loaded with the crystal seeds are placed again in 90 g of 8% copper chloride solution, 12 g of thiourea, 0.8 g of the above-prepared allyl ether-modified epoxy phosphate surfactant and 0.9 g of trisiloxane polyether phosphate surfactant are added, transferred into a high-pressure kettle, and reacted at 130°C for 10 hours; then washed with deionized water and ethanol, and dried in air to obtain sulfided copper with the three-dimensional hierarchical structure of natural butterfly wings.

[0056] Example 3 The preparation method is the same as in Example 1, except that 30 g of bisphenol A type epoxy resin, 22 g of butyl acetate, and 30 g of n-butanol are added to a four-necked flask, and the temperature is raised to 62°C and stirred for 1 hour; 18 g of allyl glycidyl ether is added, and the reaction is carried out for 2.5 hours under the action of 3.0 g of boron trifluoride etherate; the system is cooled to 50°C, 10 g of phosphorus pentoxide is added in batches, and then the reaction is carried out for 3 hours at 105°C under stirring and reflux. Separately, 22 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 55 g of isopropyl alcohol are added to a high-pressure reaction kettle, and after stirring and dissolution, 0.12 g of chloroplatinic acid isopropanol solution is added; 35 g of allyl polyether is added dropwise, and the reaction is carried out for 4 hours at 82°C. The polyether-modified trisiloxane is obtained, which is transferred to a three-necked flask, 12 g of phosphorus pentoxide is added, and the reaction is carried out for 6 hours at 91°C under nitrogen protection. 30 g of butterfly wings are soaked in ethanol for 4 hours, then washed with distilled water, and dried in air; the dried butterfly wings are placed in a 120 g of 20% ethylenediaminetetraacetic acid solution, pretreated at 140°C for 3 hours; washed with water and dried, then placed in a 90 g of 12% copper nitrate solution, soaked at 70°C for 3 hours; washed with ethanol, then immersed in a 60 g of 1.2% sodium sulfide solution, and reacted at room temperature for 2.5 hours to form CuS crystal seeds; the butterfly wings loaded with the crystal seeds are placed again in a 110 g of 12% copper nitrate solution, 18 g of thiourea, 1.2 g of the above-prepared allyl ether-modified epoxy phosphate surfactant, and 1.1 g of trisiloxane polyether phosphate surfactant are added, and the reaction is carried out for 6 hours at 170°C in a high-pressure kettle; then washed with deionized water and ethanol, and dried in air to obtain copper sulfide with the three-dimensional hierarchical structure of natural butterfly wings.

[0057] Example 4 The preparation method is the same as that in Example 1, except that 22 g of bisphenol A type epoxy resin, 19 g of butyl acetate and 22 g of n-butanol are added into a four-necked flask, and stirred at 59°C for 1.2 hours; 14 g of allyl glycidyl ether is added, and reacted for 1.8 hours under the action of 2.2 g of boron trifluoride etherate; the system is cooled to 42°C, 7 g of phosphorus pentoxide is added in batches, and then stirred and refluxed at 98°C for 3.2 hours to prepare an allyl ether modified epoxy phosphate surfactant. 19 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 48 g of isopropyl alcohol are added into an autoclave, stirred and dissolved, and then 0.09 g of chloroplatinic acid isopropanol solution is added; 28 g of allyl polyether is added dropwise, and reacted at 79°C for 4.5 hours to obtain a polyether modified trisiloxane; it is transferred into a three-necked flask, 9 g of phosphorus pentoxide is added, and reacted at 89.5°C under nitrogen protection for 7.5 hours to prepare a trisiloxane polyether phosphate surfactant. 22 g of butterfly wings are soaked in ethanol for 2.5 hours, washed with distilled water, and dried in air; the dried butterfly wings are placed in 90 g of a 12% ethylenediaminetetraacetic acid solution, pretreated at 110°C for 4.5 hours, washed and dried with water, and then placed in 75 g of a 9% copper sulfate solution, soaked at 55°C for 4.5 hours, washed with ethanol, and then immersed in 45 g of a 0.7% sodium sulfide solution, reacted at room temperature for 1.8 hours to form CuS crystal seeds; the butterfly wings loaded with the crystal seeds are placed again in 95 g of a 9% copper sulfate solution, 16 g of thiourea, 0.9 g of the above prepared allyl ether modified epoxy phosphate surfactant and 0.95 g of the trisiloxane polyether phosphate surfactant are added, transferred into an autoclave, and reacted at 140°C for 9 hours; washed with deionized water and ethanol, and dried in air to obtain copper sulfide with a natural butterfly wing three-dimensional hierarchical structure.

[0058] Example 5 The preparation method is the same as that in Example 1, except that 28 g of bisphenol A type epoxy resin, 21 g of butyl acetate and 28 g of n-butanol are added into a four-necked flask, and the temperature is raised to 61°C and stirred for 1.8 hours; 16 g of allyl glycidyl ether is added, and reacted for 2.2 hours under the action of 2.8 g of boron trifluoride etherate; the system is cooled to 48°C, 9 g of phosphorus pentoxide is added in batches, and then stirred and refluxed at 102°C for 3.8 hours to prepare an allyl ether modified epoxy phosphate surfactant. 21 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 52 g of isopropyl alcohol are added into an autoclave, stirred and dissolved, and then 0.11 g of chloroplatinic acid isopropanol solution is added; 32 g of allyl polyether is added dropwise, and reacted at 81°C for 5.5 hours to obtain a polyether modified trisiloxane; it is transferred into a three-necked flask, 11 g of phosphorus pentoxide is added, and reacted at 90.5°C under nitrogen protection for 6.5 hours to prepare a trisiloxane polyether phosphate surfactant. 28 g of butterfly wings are soaked in ethanol for 3.5 hours, washed with distilled water, and dried in air; the dried butterfly wings are placed in a 110 g of 18% ethylenediaminetetraacetic acid solution, pretreated at 130°C for 3.5 hours; washed and dried with water, and then placed in 85 g of 11% copper chloride solution, soaked at 65°C for 3.5 hours; washed with ethanol, and then immersed in 55 g of 1.0% potassium sulfide solution at room temperature for 2.2 hours to form CuS crystal seeds; the butterfly wings loaded with the crystal seeds are placed again in 105 g of 11% copper chloride solution, 17 g of thiourea, 1.1 g of the above prepared allyl ether modified epoxy phosphate surfactant and 1.05 g of trisiloxane polyether phosphate surfactant are added, and transferred into an autoclave, and reacted at 160°C for 7 hours; washed with deionized water and ethanol, and dried in air to obtain copper sulfide with natural butterfly wing three-dimensional hierarchical structure.

[0059] Example 6 The preparation method is the same as that of Example 1, except that 24 g of bisphenol A type epoxy resin, 20.5 g of butyl acetate, and 26 g of n-butanol are added to a four-necked flask, and the temperature is raised to 60.5°C and stirred for 1.6 hours; 15.5 g of allyl glycidyl ether is added, and the reaction is carried out for 2.1 hours under the action of 2.6 g of boron trifluoride etherate; the system is cooled to 46°C, 8.5 g of phosphorus pentoxide is added in batches, and then the reaction is carried out by stirring under reflux at 103°C for 3.3 hours to prepare an allyl ether modified epoxy phosphate surfactant. Separately, 20.5 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 53 g of isopropanol are added to a high-pressure reaction kettle, and after stirring and dissolving, 0.105 g of chloroplatinic acid isopropanol solution is added; 33 g of allyl polyether is added dropwise, and the reaction is carried out at 80.5°C for 4.8 hours to obtain a polyether modified trisiloxane; it is transferred to a three-necked flask, 10.5 g of phosphorus pentoxide is added, and the reaction is carried out at 90.2°C under nitrogen protection for 7.2 hours to prepare a trisiloxane polyether phosphate surfactant. 26 g of butterfly wings are soaked in ethanol for 3.2 hours, washed with distilled water, and dried in air; the dried butterfly wings are placed in a 115 g of 16% ethylenediaminetetraacetic acid solution and pretreated at 125°C for 4.2 hours; after washing and drying with water, they are placed in a 87 g of 10.5% copper nitrate solution and soaked at 62°C for 4.2 hours; after washing with ethanol, they are immersed in a 58 g of 0.9% sodium sulfide solution and reacted at room temperature for 2.3 hours to form CuS crystal seeds; the butterfly wings loaded with the crystal seeds are placed again in a 108 g of 10.5% copper nitrate solution, 16.5 g of thiourea, 1.15 g of the above-prepared allyl ether modified epoxy phosphate surfactant, and 1.08 g of trisiloxane polyether phosphate surfactant are added, and transferred to a high-pressure kettle for reaction at 155°C for 8.5 hours; after washing with deionized water and ethanol, and drying in air, copper sulfide with natural butterfly wing three-dimensional hierarchical structure is prepared.

[0060] The preparation method is the same as that of Example 1, except that no surfactant is added.

[0061] Comparative Example 2 The preparation method is the same as that of Example 1, except that only the allyl ether modified epoxy phosphate surfactant is added.

[0062] Comparative Example 3 The preparation method is the same as that of Example 1, except that cetyltrimethylammonium bromide is used instead of the two special surfactants.

[0063] II. Performance test and result analysis The copper sulfide with natural butterfly wing three-dimensional hierarchical structure prepared in Examples 1-3 and Comparative Examples 1-3 is tested for performance by the following methods: The material micro-morphology was observed by a field emission scanning electron microscope (FE-SEM) of SU8010 type of Japan Hitachi Company, with an accelerating voltage of 15 kV and a working distance of 8 mm. The sample was vacuum-plated with gold for 60 s before testing. The specific surface area and pore structure were tested by an ASAP 2020 full-automatic specific surface area and porosity analyzer of American Micromeritics Company. The sample was vacuum-deaerated at 150°C for 6 h, and the N2 adsorption-desorption isotherm test was performed at a liquid nitrogen temperature of 77 K. The specific surface area was calculated by the BET method, and the pore size distribution was calculated by the BJH model from the desorption branch. The crystal structure was analyzed by an X-ray diffractometer (XRD) of D / max-2500 type of Japan Rigaku Company, 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. The photocatalytic performance test: a methylene blue solution with a concentration of 20 mg / L was prepared in an amount of 200 mL, 0.1 g of the catalyst was added, and the adsorption equilibrium was reached after magnetic stirring in the dark for 30 min. Then, the photocatalytic degradation was performed under the irradiation of a 300 W xenon lamp (CEL-HXF300 of Beijing Zhongjiao Jinyuan). Every 20 min, 4 mL of the sample was taken, filtered through a 0.22 μm microporous filter membrane, and the absorbance was measured at 664 nm by a TU-1901 ultraviolet-visible spectrophotometer of Beijing Puzan. The degradation rate calculation formula was η = (1-C / C0) x 100%, wherein C0 was the initial concentration, and C was the concentration after the reaction. The electrochemical performance was tested by a CHI660E electrochemical workstation of Shanghai Chenhua. The three-electrode system: the working electrode was a copper sulfide with a natural butterfly wing three-dimensional hierarchical structure prepared according to Examples 1-3 and Comparative Examples 1-3, which was mixed and ground with acetylene black and polyvinylidene fluoride at a mass ratio of 8:1:1, coated on a 1 cm x 1 cm nickel foam (the loading amount was about 2 mg), and pressed into a sheet under a pressure of 10 MPa; the counter electrode was a platinum sheet electrode (1 cm x 1 cm); the reference electrode was a saturated calomel electrode (SCE); and the electrolyte was a 1 mol / L Na2SO4 solution. The cyclic voltammetry test was performed at a scanning rate of 5-100 mV / s and a potential window of -0.2-0.8 V. The constant current charge and discharge test was performed at a current density of 1-10 A / g and a potential window of -0.2-0.8 V. The specific capacitance calculation formula was C = IΔt / (mΔV), wherein I was the discharge current (A), Δt was the discharge time (s), m was the active material mass (g), and ΔV was the potential window (V). The cycle stability test was performed at a current density of 5 A / g for 5,000 charge and discharge cycles.

[0064] Table 1: Performance test results of each example and comparative example

[0065] As can be seen from Table 1, the test results fully prove that the four technical problems existing in the prior art copper sulfide material are effectively solved by the synergistic combination of the allyl ether modified epoxy phosphate surfactant and the trisiloxane polyether phosphate surfactant in the embodiments 1-3 of the present application. First, in terms of specific surface area, the embodiment 1 reaches 285 m² / g, which is more than 110% higher than 135 m² / g of the comparative example 1, which is due to the fact that the two surfactants precisely guide the copper sulfide to grow along the butterfly wing three-dimensional skeleton, perfectly copying the multi-stage channel structure thereof, while the comparative material collapses due to the lack of effective morphology control. In terms of active sites, the photocatalytic degradation rate of the embodiment 1 is as high as 98.5%, which is much higher than 65.3% of the comparative example 1, because the specially-made surfactant makes the material form rich mesoporous and macroporous structures, providing sufficient channels and active centers for reactant transmission and surface reaction.

[0066] In terms of morphology control accuracy, the embodiment material exhibits a highly consistent hierarchical structure, while the photocatalytic degradation rate of the comparative example 2 using only a single surfactant is reduced to 82.4%, which proves that the synergistic effect of the two surfactants is indispensable: the allyl ether modified epoxy phosphate surfactant controls the crystal growth direction through the specific binding of its phosphate group to the crystal surface; and the trisiloxane polyether phosphate surfactant guides the ordered self-assembly of nanosheets through its special trisiloxane structure. This double regulation mechanism ensures that the fine structure of the butterfly wing template is not damaged during the copying process.

[0067] In terms of structural stability, the capacity of the embodiment 1 remains 92.3% after 5000 charge-discharge cycles, while the stability of the comparative example 3 using the conventional surfactant hexadecyl trimethyl ammonium bromide is reduced to 80.3%, because the specially-made surfactant forms a stable connection with the copper sulfide crystal through strong chemical bonding, effectively buffering the volume change during the charge-discharge process and preventing structural collapse. At the same time, the uniform pore size distribution and good mechanical strength of the embodiment material further guarantee the long-term cycle stability.

[0068] In summary, the present application successfully realizes the accurate regulation of the multi-stage structure of the copper sulfide material from the nanometer to the micron scale through the synergistic effect of the two specially-made surfactants, completely solves the technical problems that the traditional method cannot simultaneously consider high specific surface area, rich active sites, accurate morphology control and long-term stability, and provides a new solution for the controllable preparation of high-performance copper sulfide materials.

[0069] The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the patent scope of the present application. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the protection scope of the present application.

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-immersing the butterfly wing loaded with CuS crystal seeds in a copper ion solution, adding thiourea, an allyl ether modified epoxy phosphate surfactant and a trisiloxane polyether phosphate surfactant, and transferring the reaction system to an autoclave for constant temperature reaction at 100-180 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, 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.

5. The method of producing copper sulfide having a natural three-dimensional hierarchical configuration of butterfly wings according to claim 4, characterized by, In step A1, the stirring time at a temperature of 58-62 DEG C is 1-2 h.

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

7. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 1, characterized in that, 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.

8. The method for preparing copper sulfide with a natural butterfly wing three-dimensional hierarchical structure according to claim 7, characterized in that, In step B1, the reaction time at a temperature of 78-82 DEG C is 4-6 h.

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

10. 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 according to the preparation method of the copper sulfide with natural butterfly wing three-dimensional hierarchical configuration according to any one of claims 1-9.

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