Preparation method of molybdenum disulfide material with biological fine hierarchical structure morphology

Abstract

The application provides a preparation method of a molybdenum disulfide material with a biological fine hierarchical structure, relates to the technical field of nanometer materials, and comprises the following steps: preparing biological wings as a biological template; using an ethylenediamine tetraacetic acid solution to pretreat the biological template; and growing molybdenum disulfide on the pretreated biological template by using a hydrothermal method to obtain a biological form fine hierarchical structure molybdenum disulfide material, wherein the application uses a large number of biological templates with fine hierarchical structures existing in nature as templates, and realizes the preparation of the fine hierarchical structure molybdenum disulfide material by using the hydrothermal method; the prepared metal material inherits the fine structure characteristics of the original biological template, and has wide application value in the fields of photoelectrons, photocatalysis and magnetic properties; compared with the original biological template, the thickness of the molybdenum disulfide layer can be further controlled by adjusting the hydrothermal time and temperature of the hydrothermal method, so that the multi-scale hierarchical fine structure molybdenum disulfide material with different biological form structures can be prepared.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, specifically to a method for preparing molybdenum disulfide materials with a finely hierarchical biological structure. Background Technology

[0002] Molybdenum disulfide (MoD) materials with micro / nano structures have attracted widespread attention in the fields of nanotechnology and porous materials science in recent years. MoD possesses excellent properties such as a tunable bandgap structure, high mechanical strength, excellent light absorption characteristics, and high catalytic activity, making it suitable for important applications in micro / nanoelectronic devices, photodetectors, and energy storage catalytic systems. For example, surface-enhanced Raman scattering (SERS) plays a crucial role in environmental, medical, and materials science fields. Furthermore, the quantum confinement effect, direct bandgap characteristics, and active edge sites exhibited by monolayer or few-layer MoD exhibit great promise for applications in novel transistors, flexible electronics, high-efficiency optoelectronic devices, and advanced catalysis. For instance, monolayer MoD exhibits a direct bandgap and significant valley polarization characteristics. Based on these characteristics, scientists have observed the valley Hall effect and valley photocurrent in two-dimensional heterostructures and field-effect devices. Such valley-electronic devices will exhibit information processing methods completely different from traditional charge-based electronics, potentially driving the development of entirely new fields of spintronics and quantum information technology. Furthermore, by utilizing the atomic-level thickness, high surface activity, and strong light-matter interaction of monolayer molybdenum disulfide, high on / off ratio transistors, ultrasensitive photodetectors, efficient photoluminescence / quantum emission, and excellent hydrogen evolution reaction catalysis effects can be achieved. This has greatly promoted the development of basic and applied research in two-dimensional materials science and technology, such as ultrathin flexible electronics, low-power logic circuits, single-light sources, high-efficiency energy conversion (hydrogen production by water electrolysis, batteries), nanosensing, and other cutting-edge application technology fields.

[0003] In recent years, high-temperature solid-state methods, chemical vapor deposition, hydrothermal / solvothermal methods, and ammonium thiomolybdate thermal decomposition methods have been commonly used to prepare molybdenum disulfide materials suitable for various fields. However, methods for preparing complex molybdenum disulfide are relatively scarce, with most research focusing on 2D or thin-layer molybdenum disulfide. As research has progressed, studies on 3D molybdenum disulfide have gradually emerged, but these generally have relatively simple structures, and the preparation of fine structures faces significant technical barriers, making it difficult to meet the demands of modern high-tech development. Summary of the Invention

[0004] This invention provides a method for preparing molybdenum disulfide materials with a finely hierarchical biological structure. This method addresses the technical challenges that arise from the emerging research on 3D molybdenum disulfide, which generally presents relatively simple structures and faces significant technical barriers in the preparation of fine structures, making it difficult to meet the needs of modern high-tech development.

[0005] To address the aforementioned technical problems, this invention discloses a method for preparing molybdenum disulfide materials with a finely hierarchical biological structure, comprising the following steps:

[0006] Step 1: Prepare biological wings as a biological template;

[0007] Step 2: Pretreatment of the biological template with ethylenediaminetetraacetic acid solution;

[0008] Step 3: Molybdenum disulfide is grown on the pretreated biological template using a hydrothermal method to obtain molybdenum disulfide material with a fine hierarchical structure of biological morphology.

[0009] Preferably, biological wings include any one of butterfly wings, dragonfly wings, and moth wings.

[0010] Preferably, the ethylenediaminetetraacetic acid solution comprises a mixed solution of ethylenediaminetetraacetic acid and a solvent, wherein the volume ratio of ethylenediaminetetraacetic acid to the solvent is 1-10:1-100.

[0011] Preferably, the solvent includes any one or more combinations of DMF, tetrahydrofuran, ethanol, and methanol.

[0012] Preferably, the pretreatment method in step 2 is to first immerse the biological template in a high-temperature ethylenediaminetetraacetic acid solution for 3-24 hours, then wash the immersed biological template with a solvent, and finally air dry it naturally in the air.

[0013] Preferably, the temperature of the high-temperature ethylenediaminetetraacetic acid solution is 80℃-300℃.

[0014] Preferably, in step 3, the hydrothermal method involves placing the pretreated biological template into a hydrothermal solution, then placing the hydrothermal solution containing the biological template into a hydrothermal reactor and heating it to 130℃-220℃ for 12h-30h until it returns to room temperature. After that, the biological template is washed with ethanol and then dried in the air to obtain a molybdenum disulfide material with a fine hierarchical structure of biological morphology.

[0015] Preferably, the hydrothermal solution comprises any one or more combinations of the following: an aqueous solution of ammonium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of sodium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of potassium molybdate and thiourea with a concentration of 0.1wt%-10wt%; and an aqueous solution of phosphomolybdic acid and thiourea with a concentration of 0.1wt%-10wt%.

[0016] Preferably, the mass ratio of molybdenum reagent to thiourea reagent is 1-10:1-10, and the molybdenum reagent includes any one or more combinations of ammonium molybdate, sodium molybdate, and potassium molybdate.

[0017] Preferably, the pH value of the hydrothermal solution is 1-13, and the pH value of the hydrothermal solution can be adjusted by adding hydrochloric acid or ammonia.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] This invention uses the wings of organisms with fine hierarchical structures, which are abundant in nature, as templates. A hydrothermal method is employed to prepare molybdenum disulfide materials with fine hierarchical structures, creating a novel method for rapid, simple, inexpensive, and effective preparation of such materials. The prepared metallic materials inherit the fine structural characteristics of the original biological template and have broad application value in the fields of optoelectronics, photocatalysis, and magnetic properties. Compared to the original biological template, the thickness of the molybdenum disulfide layer can be further controlled by adjusting the concentration of the hydrothermal solution, achieving the goal of preparing multi-scale hierarchical fine-structure molybdenum disulfide materials with different biological morphological structures. Attached Figure Description

[0020] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0021] Figure 1 This is a scanning electron microscope image of the molybdenum disulfide material with a biological morphological hierarchical structure in Example 2;

[0022] Figure 2 The energy spectrum of the molybdenum disulfide material with a hierarchical structure of biological morphology in Example 2 is shown.

[0023] Figure 3 yes Figure 1 Low magnification chart;

[0024] Figure 4 This is a scanning electron microscope image of the molybdenum disulfide material with a biological morphological hierarchical structure in Example 3;

[0025] Figure 5 The energy spectrum of the molybdenum disulfide material with a hierarchical structure of biological morphology in Example 3 is shown.

[0026] Figure 6 This is a scanning electron microscope image of the molybdenum disulfide material with a biological morphological hierarchical structure in Example 4;

[0027] Figure 7 This is a scanning electron microscope image of the molybdenum disulfide material with a biological morphological hierarchical structure in Example 5. Detailed Implementation

[0028] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0029] Furthermore, in this invention, the use of terms such as "first" and "second" is for descriptive purposes only and does not specifically refer to any order or sequence, nor is it intended to limit the invention. They are merely used to distinguish components or operations described using the same technical terms and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the technical solutions and features of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. If a combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0030] The present invention provides the following embodiments.

[0031] Example 1: This embodiment of the invention provides a method for preparing molybdenum disulfide materials with a finely hierarchical biological structure, comprising the following steps:

[0032] Step 1: Prepare biological wings as a biological template;

[0033] Step 2: Pretreatment of the biological template with ethylenediaminetetraacetic acid solution;

[0034] Step 3: Molybdenum disulfide is grown on the pretreated biological template using a hydrothermal method to obtain molybdenum disulfide material with a fine hierarchical structure of biological morphology;

[0035] Biological wings include any one of the following: butterfly wings, dragonfly wings, and moth wings;

[0036] The ethylenediaminetetraacetic acid solution comprises a mixture of ethylenediaminetetraacetic acid and a solvent, wherein the volume ratio of ethylenediaminetetraacetic acid to solvent is 1-10:1-100;

[0037] Solvents include any one or more combinations of DMF, tetrahydrofuran, ethanol, and methanol;

[0038] The pretreatment method in step 2 is to first immerse the biological template in a high-temperature ethylenediaminetetraacetic acid solution for 3-24 hours, then wash the immersed biological template with solvent, and finally let it air dry naturally.

[0039] The temperature range for high-temperature ethylenediaminetetraacetic acid solutions is 80℃-300℃;

[0040] Step 3, the hydrothermal method, involves placing the pretreated biological template into a hydrothermal solution, then placing the hydrothermal solution containing the biological template into a hydrothermal reactor and heating it to 130℃-220℃ for 12h-30h. After the temperature returns to room temperature, the biological template is washed with ethanol and then dried in the air to obtain molybdenum disulfide material with a fine hierarchical structure of biological morphology.

[0041] The hydrothermal solution includes any one or more combinations of the following: an aqueous solution of ammonium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of sodium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of potassium molybdate and thiourea with a concentration of 0.1wt%-10wt%; and an aqueous solution of phosphomolybdic acid and thiourea with a concentration of 0.1wt%-10wt%.

[0042] The mass ratio of molybdenum reagent to thiourea reagent is 1-10:1-10, and the molybdenum reagent includes any one or more combinations of ammonium molybdate, sodium molybdate, and potassium molybdate.

[0043] The pH value of the hydrothermal solution is 1-13, and it can be adjusted by adding hydrochloric acid or ammonia.

[0044] The working principle of the above technical solution is as follows:

[0045] Ethylenediaminetetraacetic acid (EDTA) is pretreated to modify the organic matter surface of the biological wing. Then, the carboxyl groups on the EDTA surface are used to capture the Mo ions slowly generated during the reaction and anchor them to the surface of the butterfly wing, thereby nucleating and generating patches of molybdenum disulfide, which eventually cover the entire biological wing.

[0046] Example 2: Based on Example 1, as follows Figures 1-3 As shown, natural Heliotropium purpureus butterfly was selected as a template. After immersion in a mixed solution of ethylenediaminetetraacetic acid and DMF at 110℃ for 6 hours, it was washed with DMF and then air-dried naturally. Subsequently, it was placed in a hydrothermal solution composed of 0.5g ammonium molybdate, 1g thiourea, and 150mL deionized water. The hydrothermal solution containing the Heliotropium purpureus butterfly template was placed in a hydrothermal reactor and heated at 200℃ for 20 hours. After returning to room temperature, the butterfly wings were washed with ethanol and air-dried to obtain butterfly wings@molybdenum disulfide.

[0047] The working principle of the above technical solution is as follows:

[0048] pass Figure 1 The layered material distribution in the middle section indicates that the surface of the butterfly wings is composed of molybdenum disulfide (MoS2), which is evenly distributed and retains the three-dimensional microstructure of the wings. Figure 2 The energy dispersive spectroscopy (EDS) spectrum proves that the main components of the material surface are Mo and S. Figure 3 yes Figure 1The low-magnification image demonstrates the uniformity of the material preparation. If it appears very messy, it indicates poor material uniformity (i.e., poor processing). Figure 3 The orderly arrangement of the lines in the paper demonstrates the good uniformity of the molybdenum disulfide material, indicating that the preparation process of the molybdenum disulfide material in this application is stable and excellent.

[0049] Example 3: Based on Example 1, such as Figures 4-5 As shown, a natural *Heliotropium indicum* butterfly was selected as a template. After immersing in a mixed solution of ethylenediaminetetraacetic acid (EDTA) and DMF at 110°C for 6 hours, it was washed with DMF and then air-dried. Subsequently, it was placed in a hydrothermal solution consisting of 2g ammonium molybdate, 4g thiourea, and 150mL deionized water. The hydrothermal solution containing the *Heliotropium indicum* butterfly template was placed in a hydrothermal reactor and heated at 200°C for 20 hours. After returning to room temperature, the butterfly wings were washed with ethanol and then air-dried to obtain butterfly wings@molybdenum disulfide.

[0050] The working principle of the above technical solution is as follows:

[0051] pass Figure 4 The layered material distribution in the middle section indicates that the surface of the butterfly wings is composed of molybdenum disulfide (MoS2), which is evenly distributed and retains the three-dimensional microstructure of the wings. Figure 5 The energy dispersive spectroscopy (EDS) spectrum confirms that the main components of the material surface are Mo and S. Figure 4 and Figure 5 It can be seen that, under the same process conditions, increasing the concentration of potassium molybdate and thiourea aqueous solution can increase the molybdenum disulfide (MoS2) loading on the surface of butterfly wings, thus achieving the goal of controlling the thickness of the molybdenum disulfide layer.

[0052] Example 4: Based on Example 1, as follows Figure 6 As shown, natural Heliotropium purpureus butterfly was selected as a template. After immersion in a mixed solution of ethylenediaminetetraacetic acid and DMF at 110℃ for 6 hours, it was washed with DMF and then air-dried. Subsequently, it was placed in a hydrothermal solution composed of 0.42g phosphomolybdic acid, 1g thiourea, and 150mL deionized water. The hydrothermal solution containing the Heliotropium purpureus butterfly template was placed in a hydrothermal reactor and heated at 200℃ for 20 hours. After returning to room temperature, the butterfly wings were washed with ethanol and then air-dried to obtain butterfly wings@molybdenum disulfide.

[0053] The working principle of the above technical solution is as follows:

[0054] Depend on Figure 6 It can be seen that for the same species of butterfly wings, changing the molybdenum reagent (i.e., replacing ammonium molybdate with phosphomolybdic acid) can also achieve the same effect, demonstrating the diversity of reagent selection. Figures 1-5 The conclusion is known. Figure 6The layered material in the image is molybdenum disulfide, and the corresponding energy spectrum is not shown in the attached figure.

[0055] Example 5: Based on Example 1, as follows Figure 7 As shown, a natural citrus swallowtail butterfly was selected as a template. After being immersed in a mixed solution of ethylenediaminetetraacetic acid and DMF at 110℃ for 6 hours, it was washed with DMF and then air-dried naturally. Subsequently, it was placed in a hydrothermal solution composed of 0.5g ammonium molybdate, 1g thiourea, and 150mL deionized water. The hydrothermal solution containing the citrus swallowtail butterfly template was placed in a hydrothermal reactor and heated at 200℃ for 20 hours. After returning to room temperature, the butterfly wings were washed with ethanol and then air-dried to obtain butterfly wings@molybdenum disulfide.

[0056] The working principle of the above technical solution is as follows:

[0057] Depend on Figure 7 It can be seen that, compared with Example 2, the same process can achieve the same effect for different species of butterfly wings, demonstrating the diversity of biological template selection. Figures 1-5 The conclusion is known. Figure 7 The layered material in the image is molybdenum disulfide, and the corresponding energy spectrum is not shown in the attached figure.

[0058] Example 6: Based on Example 1, a method for analyzing the sealing performance of a hydrothermal reactor during a hydrothermal reaction process is included. The specific method includes:

[0059] Step 4: Based on the target molar amounts of each component in the hydrothermal solution that need to be consumed during the hydrothermal reaction, obtain the molar amounts of various types of liquids remaining inside the hydrothermal reactor after the hydrothermal reaction.

[0060] Step 5: Detect the maximum internal temperature of the hydrothermal reactor after the hydrothermal reaction using the temperature sensor on the reactor.

[0061] Step 6: Connect the controller to the temperature sensor on the hydrothermal reactor. The controller calculates the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction based on the molar amount of various liquids remaining inside the hydrothermal reactor after the hydrothermal reaction obtained in Step 4, the maximum temperature inside the hydrothermal reactor after the hydrothermal reaction detected in Step 5, and formula (1).

[0062] (1)

[0063] in, This represents the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction. denoted as , where is the internal volume of the hydrothermal reactor, and 'b' represents the number of different types of liquid remaining inside the reactor after the hydrothermal reaction. This represents the molar amount of type a liquid remaining inside the hydrothermal reactor after the hydrothermal reaction. This represents the molar mass of the remaining type a liquid inside the hydrothermal reactor after the hydrothermal reaction. Let be the density of the remaining type a liquid inside the hydrothermal reactor after the hydrothermal reaction, and j be the number of gas types inside the hydrothermal reactor after the hydrothermal reaction. This represents the molar amount of the i-th type of gas remaining inside the hydrothermal reactor after the hydrothermal reaction. Let be the ideal gas constant. This represents the maximum temperature inside the hydrothermal reactor after the hydrothermal reaction. The inner diameter of the hydrothermal reactor. The outer diameter of the hydrothermal reactor;

[0064] Step 7: The controller compares the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction with the yield strength of the hydrothermal reactor. If the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction is greater than the yield strength of the hydrothermal reactor, it indicates that there is a risk of deformation of the hydrothermal reactor, which will affect the sealing performance of the hydrothermal reactor.

[0065] The working principle of the above technical solution is as follows:

[0066] Based on the target molar amounts of each component in the hydrothermal solution to be consumed during the hydrothermal reaction, the molar amounts of various types of liquids remaining inside the hydrothermal reactor after the hydrothermal reaction are obtained; the maximum temperature inside the hydrothermal reactor after the hydrothermal reaction is detected by the temperature sensor on the hydrothermal reactor; the controller is electrically connected to the temperature sensor on the hydrothermal reactor, and the controller calculates the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction based on the molar amounts of various types of liquids remaining inside the hydrothermal reactor after the hydrothermal reaction obtained in step 4, the maximum temperature inside the hydrothermal reactor after the hydrothermal reaction detected in step 5, and formula (1). The controller compares the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction. The equivalent stress and yield strength of the hydrothermal reactor are considered. If the equivalent stress inside the hydrothermal reactor after the hydrothermal reaction is greater than the yield strength of the hydrothermal reactor, it indicates that the gas pressure after the hydrothermal reaction in the hydrothermal reactor is too high, which poses a risk of deformation. In fact, the gas pressure generated during the hydrothermal reaction may already pose a risk of deformation of the hydrothermal reactor, thereby affecting the sealing performance of the hydrothermal reactor. It is necessary to select a hydrothermal reactor of appropriate volume or material according to the reactants added during the hydrothermal reaction and the molar amount consumed in the reaction to ensure that the hydrothermal reactor remains sealed during the hydrothermal reaction, thereby ensuring the normal generation of the molybdenum disulfide material with a fine biological hierarchical structure as described in this application.

[0067] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing molybdenum disulfide materials with a finely hierarchical biological structure, characterized in that: Includes the following steps: Step 1: Prepare biological wings as a biological template; Step 2: Pretreatment of the biological template with ethylenediaminetetraacetic acid solution; Step 3: Molybdenum disulfide is grown on the pretreated biological template using a hydrothermal method to obtain molybdenum disulfide material with a fine hierarchical structure of biological morphology; The pretreatment method in step 2 is to first immerse the biological template in a high-temperature ethylenediaminetetraacetic acid solution for 3-24 hours, then wash the immersed biological template with solvent, and finally let it air dry naturally. Step 3, the hydrothermal method, involves placing the pretreated biological template into a hydrothermal solution, then placing the hydrothermal solution containing the biological template into a hydrothermal reactor and heating it to 130℃-220℃ for 12-30 hours until it returns to room temperature. After that, the biological template is washed with ethanol and then dried in the air to obtain molybdenum disulfide material with a fine hierarchical structure of biological morphology.

2. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 1, characterized in that: Biological wings include any of the following: butterfly wings, dragonfly wings, and moth wings.

3. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 1, characterized in that: The ethylenediaminetetraacetic acid solution comprises a mixture of ethylenediaminetetraacetic acid and a solvent, wherein the volume ratio of ethylenediaminetetraacetic acid to the solvent is 1-10:1-100.

4. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 3, characterized in that: Solvents include any one or more combinations of DMF, tetrahydrofuran, ethanol, and methanol.

5. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 1, characterized in that: The temperature range for high-temperature ethylenediaminetetraacetic acid solutions is 80℃-300℃.

6. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 1, characterized in that: The hydrothermal solution includes any one or more combinations of the following: an aqueous solution of ammonium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of sodium molybdate and thiourea with a concentration of 0.1wt%-10wt%; an aqueous solution of potassium molybdate and thiourea with a concentration of 0.1wt%-10wt%; and an aqueous solution of phosphomolybdic acid and thiourea with a concentration of 0.1wt%-10wt%.

7. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 6, characterized in that: The mass ratio of molybdenum reagent to thiourea reagent is 1-10:1-10. The molybdenum reagent includes any one or more combinations of ammonium molybdate, sodium molybdate, and potassium molybdate.

8. The method for preparing a molybdenum disulfide material with a finely hierarchical biological structure according to claim 6, characterized in that: The pH value of the hydrothermal solution is 1-13, and it can be adjusted by adding hydrochloric acid or ammonia.

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