Preparation method and application of surface-modified spherical nanoshell NiS

Abstract

This invention discloses a method for preparing surface-modified spherical hollow nanoshell NiS and its application, relating to inorganic non-metallic materials and their application in the field of passive interference technology. The prepared surface-modified spherical hollow nanoshell NiS can be used as a novel passive smoke screen interference material. Its particle surface is hydrophobically modified, making it less prone to agglomeration and exhibiting good flow properties, thus improving the compatibility of the product with equipment in practical applications. Its crystal configuration and unique hollow structure give it strong absorption and scattering capabilities. The nanometer thickness of the hollow spherical structure can excite the small size effect and quantum size effect of the material, and it has high extinction capabilities in the visible light and near-mid-far infrared bands. Compared with traditional smoke screen interference materials, it has great performance advantages, and the preparation process is simple, efficient, and low in cost.

Description

Technical Field

[0001] This invention relates to inorganic non-metallic materials and their applications in the field of passive interference technology, and particularly to a method for preparing and applying surface-modified spherical nano-shell NiS. Background Technology

[0002] With the rapid development of modern military technology, various precision-guided weapons based on optoelectronic technology are emerging. In order to counter the threat of various optoelectronic weapons, optoelectronic countermeasures technology is also developing rapidly. Among the many countermeasures methods, passive smoke screen jamming technology has become one of the key research directions in the field of optoelectronic countermeasures due to its unique advantages such as simple equipment, convenient use, low cost, and effective and reliable jamming.

[0003] However, existing smoke jamming materials have many limitations. On the one hand, most traditional smoke jamming materials can only interfere with a single frequency band. For example, traditional hexachloroethane-zinc (HC) and red phosphorus smoke generators are effective at interfering with visible light, but have little effect in the infrared band. When facing composite guided weapons that integrate multiple detection and guidance technologies, single-band jamming smoke materials are no longer sufficient to meet the complex and ever-changing application requirements. On the other hand, in order to counter multi-mode guided weapons, the current common technical approach is to combine single-band smoke jamming materials to form multi-band smoke composite materials. However, this approach has problems such as complicated processes, high costs, poor compatibility between components, and reduced average extinction ability. Therefore, it is essential to develop a new type of smoke jamming material with strong absorption or scattering capabilities for multiple electromagnetic waves (such as visible light and infrared light) across a wide range of wavelengths.

[0004] Nickel sulfide semiconductors with specific nanostructures can exhibit unique optical, electrical, and magnetic physicochemical properties due to surface effects, small size effects, and quantum size effects. They have been widely studied and applied in fields such as infrared detectors, stealth materials, solar energy storage devices, hydrodesulfurization catalysis, photoconductive materials, and electrode materials. However, there are no reports on the use of nano-hollow shell NiS materials in the field of passive interference. Summary of the Invention

[0005] In view of the above-mentioned prior art, the technical problem to be solved by the present invention is how to introduce nano-hollow NiS material into the field of passive interference to prepare passive smoke screen interference material.

[0006] To address the above problems, this invention provides a method for preparing surface-modified spherical nanoshell NiS, comprising the following steps:

[0007] S1. Prepare two mixed solutions consisting of deionized water and ethanol. Dissolve the soluble nickel salt and the bio-sulfurizing agent in the two mixed solutions respectively to obtain solution one and solution two.

[0008] S2. Mix solution one and solution two, add modifier, and stir initially to obtain a dark brown transparent precursor solution;

[0009] S3. The precursor solution is transferred to a hydrothermal synthesis reactor containing a para-polyphenol liner. The hydrothermal synthesis reactor is then placed in a homogeneous reactor. The precursor solution is thoroughly stirred under heating conditions through the heating and rotation systems of the homogeneous reactor.

[0010] S4. The hydrothermal synthesis reactor is removed from the homogeneous reactor and allowed to cool naturally to room temperature. The precipitated product is then filtered, washed with deionized water and anhydrous ethanol, and dried to obtain surface-modified spherical nano-shell NiS.

[0011] As a further supplement to this application, in step S1, the soluble nickel salt is at least one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate, and the bio-sulfurizing agent is at least one of cysteine, L-cysteine ​​or glutathione. The concentrations of the soluble nickel salt and the bio-sulfurizing agent in the corresponding mixed solution are both 0.01 mol / L to 1 mol / L.

[0012] As a further supplement to this application, the modifier in step S2 is zinc dialkyl dithiophosphate, wherein the alkyl group is at least one of isopropyl, butyl, pentyl, hexyl, octyl or benzyl, and the molar ratio of the soluble nickel salt, the bio-sulfurizing agent and the modifier is 1:1-2:0.01-0.1.

[0013] As a further supplement to this application, in step S3, the heating temperature of the homogeneous reactor is 210℃-240℃, the stirring speed is 30-60 rpm, and the stirring time is 12-24 hours.

[0014] As a further supplement to this application, in step S4, a vacuum dryer is used to dry the precipitated product, and the drying temperature is 80℃-100℃, and the drying time is 6-10 hours.

[0015] As a further supplement to this application, the surface-modified spherical hollow nanoshell NiS obtained in step S4 is a hollow spherical structure with a particle size of 0.5 μm-5 μm and a thickness on the nanometer scale. The surface of the surface-modified spherical hollow nanoshell NiS is hydrophobic.

[0016] In summary, this application provides a novel passive smoke screen interference material, namely, surface-modified spherical nano-shell NiS. The surface of the particles is hydrophobically modified, making them less prone to aggregation and exhibiting good flow properties, thus improving the compatibility of the product with equipment in practical applications. At the same time, it can excite the small size effect and quantum size effect of the material, and has high extinction ability in the visible light and near-mid-far infrared bands (0.4 μm - 25 μm). Compared with traditional smoke screen interference materials, it has great performance advantages, and the preparation method is simple, efficient and cost-effective. Attached Figure Description

[0017] Figure 1 Flowcharts for the first, second, third, and fourth embodiments of this application;

[0018] Figure 2 The XRD pattern of the product obtained in the first embodiment of this application;

[0019] Figure 3 This is a TEM image of the product obtained according to the second embodiment of this application;

[0020] Figure 4 This is the static extinction coefficient spectrum of the product obtained in the first embodiment of this application. Detailed Implementation

[0021] The four embodiments of this application will now be described in detail with reference to the accompanying drawings.

[0022] Implementation method 1:

[0023] This invention provides a method for preparing surface-modified spherical hollow nanoshell NiS. Please refer to [link to relevant documentation]. Figure 1 This includes the following steps:

[0024] S1. Prepare two mixed solutions consisting of deionized water and ethanol. Dissolve the soluble nickel salt and the bio-sulfurizing agent in the two mixed solutions respectively to obtain solution one and solution two.

[0025] The volume ratio of deionized water to ethanol in both mixed solutions is 1:1. The soluble nickel salt is at least one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate, and the bio-sulfurizing agent is at least one of cysteine, L-cysteine ​​or glutathione. The concentrations of the soluble nickel salt and the bio-sulfurizing agent in the corresponding mixed solutions are both 0.01 mol / L to 1 mol / L.

[0026] S2. Mix solution one and solution two, add modifier, and stir initially to obtain a dark brown transparent precursor solution;

[0027] The modifier is zinc dialkyl dithiophosphate, wherein the alkyl group is at least one of isopropyl, butyl, pentyl, hexyl, octyl or benzyl, and the molar ratio of soluble nickel salt, bio-sulfurizing agent and modifier is 1:1 to 2:0.01 to 0.1.

[0028] S3. Transfer the precursor solution to a hydrothermal synthesis reactor containing a para-polyphenol liner, and then place the hydrothermal synthesis reactor into a homogeneous reactor. Through the heating and rotation systems of the homogeneous reactor, the precursor solution is fully stirred under heating conditions, wherein the heating temperature is 210℃-240℃, the stirring speed is 30-60 rpm, and the stirring time is 12-24 hours.

[0029] S4. Remove the hydrothermal synthesis reactor from the homogeneous reactor and allow it to cool naturally to room temperature. Filter the precipitate and wash it with deionized water and anhydrous ethanol. Finally, dry the precipitate in a vacuum dryer at a temperature of 80℃-100℃ for 6-10 hours. After drying, surface-modified spherical nano-shell NiS is obtained.

[0030] The surface-modified spherical hollow-shell NiS obtained above has a hollow spherical structure with a particle size of 0.5 μm-5 μm and a thickness on the nanometer scale. The surface of the particles is hydrophobically modified, making them less prone to aggregation and exhibiting good flow properties, thus improving the compatibility of the product with equipment in practical applications. It also has strong absorption and scattering capabilities in a wide wavelength range (visible and infrared), which is directly related to its crystal configuration and unique hollow structure. The shell thickness of the hollow spherical structure is on the nanoscale, which can excite the small size effect and quantum size effect of the material, enabling the material to exhibit extremely strong visible light and infrared absorption performance. At the same time, the hollow spherical structure can cause multiple scattering of electromagnetic waves on the shell, enhancing the material's extinction ability.

[0031] The second implementation method:

[0032] Based on the first embodiment, this embodiment makes the following specific adjustments: 3.5 mmol of nickel acetate and 3.5 mmol of L-cysteine ​​are dissolved in a 1:1 mixture of deionized water and ethanol in 40 mL of water to obtain solution one and solution two. The two solutions are mixed, and 0.35 mmol of zinc butyl-octyl dithiophosphate is added. The mixture is stirred for 4 hours. The resulting dark brown transparent precursor solution is transferred to a hydrothermal synthesis reactor lined with para-polyphenol. The mixture is stirred at 220°C for 24 hours at a stirring speed of 60 rpm. After natural cooling to room temperature, the precipitate is filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 80°C for 10 hours to obtain the product.

[0033] The third implementation method:

[0034] Based on the first embodiment, this embodiment makes the following specific adjustments: 5 mmol of nickel sulfate and 10 mmol of glutathione are dissolved in a 1:1 mixture of 40 mL of deionized water and ethanol to obtain solution one and solution two. The two solutions are mixed, and 0.1 mmol of zinc di-octyl dithiophosphate is added. The mixture is stirred for 4 hours, and the resulting dark brown transparent precursor solution is transferred to a hydrothermal reactor lined with para-polyphenol. The reactor is stirred at 240°C for 12 hours at a stirring speed of 30 rpm. After natural cooling to room temperature, the precipitate is filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 100°C for 6 hours to obtain the product.

[0035] The fourth implementation method:

[0036] Based on the first embodiment, this embodiment makes the following specific adjustments: 3 mmol of nickel nitrate and 4.5 mmol of L-cysteine ​​are dissolved in a 1:1 mixture of deionized water and ethanol to obtain solution one and solution two. The two solutions are mixed, and 0.6 mmol of zinc isopropyl-octyl dithiophosphate is added. The mixture is stirred for 4 hours, and the resulting dark brown transparent precursor solution is transferred to a hydrothermal reactor lined with para-polyphenol. The reactor is stirred at 230°C for 18 hours at a stirring speed of 30 rpm. After natural cooling to room temperature, the precipitate is filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 90°C for 8 hours to obtain the product.

[0037] The final products obtained from the first, second, and third embodiments were all subjected to the following tests:

[0038] I. X-ray diffraction (XRD) test;

[0039] II. Broadband (Visible-Near-Mid-Far Infrared) Extinction Coefficient Test;

[0040] III. Transmission Electron Microscopy (TEM) Test.

[0041] Some of the test results are as follows:

[0042] Figure 2 The XRD pattern of the product obtained in the first embodiment shows that the product is a NiS phase, and the position and intensity of its diffraction peaks correspond perfectly with the position and intensity of the peaks in the JCPDS (No. 50-1791) card.

[0043] Figure 3The image shows a TEM image of the product obtained in the second embodiment. The microstructure of the product is a uniformly sized spherical shell structure with a shell wall thickness of about 50 nm to 80 nm.

[0044] Figure 4 This is the static extinction coefficient spectrum of the product obtained in the first embodiment. The graph shows that the product exhibits high extinction capability across a wavelength range of 0.4 μm to 25 μm. The material shows the strongest extinction capability in the visible and near-infrared bands, with a maximum extinction coefficient of approximately 15000 cm⁻¹. 2 / g, corresponding to a wavelength of 0.8 μm, this material exhibits the second highest extinction ability in the mid-infrared band and the lowest extinction ability in the long-infrared band, with a minimum extinction coefficient of approximately 1000 cm⁻¹. 2 / g, corresponding to a wavelength of 25 μm.

[0045] This invention yields a novel passive smoke screen interference material, namely, surface-modified spherical nanoshell NiS, through the above preparation process. This material exhibits high extinction capabilities in both the visible light and near-mid-far-infrared bands (0.4 μm - 25 μm), demonstrating significant performance advantages compared to traditional smoke screen interference materials. The preparation method is simple, efficient, and cost-effective.

[0046] In light of current practical needs, the above-described embodiments adopted in this application are not limited to these. Any changes made within the scope of knowledge possessed by those skilled in the art without departing from the concept of this application still fall within the protection scope of this invention.

Claims

1. A method for preparing surface-modified spherical hollow nanoshell NiS, characterized in that: Includes the following steps: S1. Prepare two mixed solutions consisting of deionized water and ethanol. Dissolve the soluble nickel salt and the bio-sulfurizing agent in the two mixed solutions respectively to obtain solution one and solution two. S2. Mix solution one and solution two, add modifier, and stir initially to obtain a dark brown transparent precursor solution; S3. The precursor solution is transferred to a hydrothermal synthesis reactor containing a para-polyphenol liner. The hydrothermal synthesis reactor is then placed in a homogeneous reactor. The precursor solution is thoroughly stirred under heating conditions through the heating and rotation systems of the homogeneous reactor. S4. The hydrothermal synthesis reactor is removed from the homogeneous reactor and allowed to cool naturally to room temperature. The precipitated product is then filtered, washed with deionized water and anhydrous ethanol, and dried to obtain surface-modified spherical nano-shell NiS.

2. The method for preparing surface-modified spherical hollow nanoshell NiS according to claim 1, characterized in that: In step S1, the soluble nickel salt is at least one of nickel sulfate, nickel chloride, nickel nitrate, or nickel acetate, and the bio-sulfurizing agent is at least one of cysteine, L-cysteine, or glutathione. The concentrations of the soluble nickel salt and the bio-sulfurizing agent in the corresponding mixed solution are both 0.01 mol / L to 1 mol / L.

3. The method for preparing surface-modified spherical hollow nanoshell NiS according to claim 1, characterized in that: The modifier in step S2 is zinc dialkyl dithiophosphate, wherein the alkyl group is at least one of isopropyl, butyl, pentyl, hexyl, octyl or benzyl, and the molar ratio of the soluble nickel salt, the bio-sulfurizing agent and the modifier is 1:1-2:0.01-0.

1.

4. The method for preparing surface-modified spherical hollow nanoshell NiS according to claim 1, characterized in that: The heating temperature of the homogeneous reactor in step S3 is 210℃-240℃, the stirring speed is 30-60 rpm, and the stirring time is 12-24 hours.

5. The method for preparing surface-modified spherical hollow nanoshell NiS according to claim 1, characterized in that: In step S4, a vacuum dryer is used to dry the precipitated product at a temperature of 80℃-100℃ for 6-10 hours.

6. The method for preparing surface-modified spherical hollow nanoshell NiS according to claim 1, characterized in that: The surface-modified spherical hollow nanoshell NiS obtained in step S4 is a hollow spherical structure with a particle size of 0.5μm-5μm and a thickness on the nanometer scale. The surface of the surface-modified spherical hollow nanoshell NiS is hydrophobic.

7. An application of surface-modified spherical hollow nanoshell NiS prepared by the method according to any one of claims 1-6, characterized in that: It is applied to passive interference technology.

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