A kind of efficient preparation method of purple phosphorus-based material

Abstract

The present invention belongs to the technical field of phosphorus chemical industry, and relates to an efficient preparation method of a purple phosphorus-based material. The present invention uses a phosphorus source as a reactant, an ammonium salt as a catalyst, mixes the phosphorus source and the ammonium salt under low oxygen conditions, heats the reaction, and obtains the purple phosphorus-based material after cooling. By using the ammonium salt as a catalyst, the conversion of the phosphorus source to the purple phosphorus-based material is promoted under oxygen-free and high temperature conditions, and the generation of harmful byproducts is reduced. At the same time, the ammonium salt is used as a catalyst, which is easily decomposed into gas in the reaction, and will not be sintered and deactivated at high temperature, thereby reducing production costs, improving resource utilization efficiency, and being easy to separate from the product, improving the quality of the product, realizing efficient and low-cost industrial production of purple phosphorus-based materials, and then promoting the wide application of purple phosphorus-based materials in multiple fields such as energy storage, electronic devices, and catalytic reactions.

Description

Technical Field

[0001] The invention relates to the technical field of phosphorus chemical industry, and in particular to a method for efficiently preparing a purple phosphorus-based material. Background Art

[0002] Purple phosphorus, as one of the allotropes of phosphorus, is a new type of two-dimensional material that is more stable than black phosphorus. A large number of theoretical and experimental results show that purple phosphorus has many excellent properties, such as semiconductor properties, high thermal conductivity, high carrier mobility, high mechanical strength, high transparency, high quantum efficiency, and good biocompatibility. Purple phosphorus-based materials, as a class of compounds or mixtures with purple phosphorus as the main component, not only have the excellent properties of purple phosphorus, but also show better physical and chemical properties through combination with other elements. They are widely used in many fields such as energy, electronics, and catalysis. However, purple phosphorus-based materials still face challenges in efficient preparation and cost-effectiveness, which limits the widespread application of purple phosphorus-based materials in the industrial field and also affects their application prospects in the broader market.

[0003] Existing methods for preparing purple phosphorus-based materials mainly include high-temperature melting method, chemical vapor deposition method (CVD), mechanical grinding method, solvent thermal method and mineralization method. Although the high-temperature melting method is simple to operate, it consumes a lot of energy, has high requirements on equipment, and has potential safety hazards. The mechanical grinding method has low cost, but low yield, and is easy to introduce impurities. The solvent thermal method is relatively environmentally friendly, but the reaction conditions are difficult to control and the yield is low. Although the chemical vapor deposition method can obtain high-quality purple phosphorus crystals, the preparation process is complicated, and there are problems such as catalyst sintering deactivation and product separation difficulties, which affect the purity and quality of the product. The mineralization method has the advantages of good crystal form of the prepared product and high reproducibility, and is the most promising method for large-scale preparation of purple phosphorus-based materials. However, most of the above methods for preparing purple phosphorus-based materials have the problems of long preparation process and low product quality, which limits the application and development of purple phosphorus-based materials.

[0004] In view of the limitations of existing technologies, there is an urgent need to develop a new and efficient preparation method for purple phosphorus-based materials. Summary of the invention

[0005] The object of the present invention is to provide a kind of efficient preparation method of purple phosphorus-based materials, utilize ammonium salt as catalyst, promote the conversion of phosphorus source to purple phosphorus-based materials under oxygen-free and high temperature conditions, reduce the generation of harmful byproducts, to solve the problems existing in the above-mentioned prior art. At the same time, ammonium salt is used as catalyst, and it is easily decomposed into gas in the reaction, so that the reaction process has higher reaction rate and selectivity, promotes phosphorus atom rearrangement to generate purple phosphorus-based materials, and ammonium salt is not easy to combine with product to generate impurities after decomposition, improves the quality of product. And the catalyst will not be sintered and deactivated at high temperature, improves the utilization efficiency of resources, reduces production cost, realizes the efficient and low-cost industrial production of purple phosphorus-based materials, and then promotes the wide application of purple phosphorus-based materials in multiple fields such as energy storage, electronic devices, catalytic reaction, etc.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention is to provide an efficient preparation method of purple phosphorus-based materials, the steps comprising:

[0008] A phosphorus source is used as a reactant and an ammonium salt is used as a catalyst. The phosphorus source and the ammonium salt are mixed under low-oxygen conditions, heated for reaction, and cooled to obtain the purple phosphorus-based material.

[0009] During the heating process, the material is activated and a chemical reaction occurs. Phosphorus atoms are rearranged under the catalytic action of ammonium salts to generate purple phosphorus-based materials.

[0010] Furthermore, the phosphorus source is white phosphorus and / or red phosphorus.

[0011] Furthermore, the ammonium salt is ammonium chloride.

[0012] As a new type of catalyst, ammonium salt can decompose rapidly under high temperature conditions, promoting the recombination of phosphorus atoms to form compounds mainly composed of purple phosphorus. This reaction process can realize the preparation of purple phosphorus-based materials under relatively mild conditions, greatly shortening the preparation time of purple phosphorus-based materials, improving the yield and quality of the product, and reducing production costs, laying the foundation for subsequent exploration of the performance and application of purple phosphorus-based materials.

[0013] Furthermore, the mass ratio of the phosphorus source to the ammonium salt is 1:1-5.

[0014] Furthermore, the oxygen-poor condition is provided by a vacuum or inert atmosphere.

[0015] Preferably, the inert atmosphere is an argon atmosphere or a nitrogen atmosphere.

[0016] Furthermore, the temperature of the heating reaction is 450-550°C, the heating rate is 2-5°C / min, the time is not less than 12h, and the pressure is not less than 5atm.

[0017] The temperature range of the above-mentioned heating reaction can ensure the effective conversion of the phosphorus source and avoid the decomposition of the product due to excessively high temperature. During the heating process, the hydrogen chloride gas and ammonia generated by the decomposition of the ammonium salt react with the phosphorus source to promote the conversion of the phosphorus source to the purple phosphorus-based material. The catalytic effect of the ammonium salt not only reduces the activation energy of the reaction, but also increases the reaction rate, which is beneficial to the conversion of the material.

[0018] The second technical solution of the present invention is to provide a purple phosphorus-based material prepared by the above preparation method.

[0019] The third technical solution of the present invention is to provide an application of the above-mentioned purple phosphorus-based material in the fields of energy, electronics and catalysis.

[0020] The present invention discloses the following technical effects:

[0021] The invention provides a novel and efficient preparation method for purple phosphorus-based materials, which utilizes ammonium salt as a catalyst to achieve efficient and low-cost preparation of purple phosphorus-based materials. The method of the invention not only improves the production efficiency of purple phosphorus-based materials, but also reduces energy consumption and quality impact in the production process. The preparation process is simple and efficient, which is of great significance for promoting the practical application of purple phosphorus-based materials.

[0022] The present invention adopts ammonium salt as a catalyst, improves the preparation yield of purple phosphorus-based materials by regulating the reaction rate and selectivity, greatly shortens the preparation time, and has a simple and efficient preparation process, which is of great significance for promoting the practical application of purple phosphorus-based materials. The preparation method provides ideas for the preparation of other heterojunction materials and the improvement of their performance.

[0023] The efficient preparation of purple phosphorus-based materials by the present invention helps to improve their production efficiency and the feasibility of large-scale preparation. The efficient preparation technology can accelerate the research and development transformation and commercialization process of purple phosphorus-based materials and promote the market promotion and industrial development of related technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 This is a schematic diagram of the process flow of Example 1;

[0026] Figure 2 The XRD pattern of the purple phosphorus-based material prepared in Example 1;

[0027] Figure 3 This is the Raman spectrum of the purple phosphorus-based material prepared in Example 1;

[0028] Figure 4 The scanning electron microscope images and element distribution maps of the purple phosphorus-based material prepared in Example 1, wherein (a), (b) and (c) are SEM images, (d) is an EDS image, (e), (f) and (g) are element distribution maps, and (h) is a HR-TEM image. DETAILED DESCRIPTION

[0029] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0030] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0031] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0032] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0033] The words “include,” “including,” “have,” “contain,” etc. used in the present invention are open-ended terms, meaning including but not limited to.

[0034] In some embodiments, a novel and efficient method for preparing purple phosphorus-based materials is provided, the steps comprising:

[0035] S1. Raw material preparation: Select a pure phosphorus source (white phosphorus and / or red phosphorus) as the starting material, and weigh an appropriate amount of ammonium salt (ammonium chloride) according to a certain ratio according to the required output of purple phosphorus-based materials;

[0036] S2, mixing: mixing the phosphorus source and the ammonium salt under vacuum or inert atmosphere (nitrogen or argon); the mixing ratio is preferably a mass ratio of the phosphorus source to the ammonium salt of 1:1 to 5 to ensure sufficient conversion of the phosphorus source;

[0037] S3. Heating: Heat the mixed raw materials to 450°C to 550°C in a vacuum environment (heating rate of 5°C / min, time of not less than 12 hours, pressure of not less than 5atm). This temperature range can ensure the effective conversion of the phosphorus source and avoid excessive decomposition of the product;

[0038] S4. Catalytic conversion: During the heating process, the hydrogen chloride gas and ammonia generated by the decomposition of the ammonium salt react with the phosphorus source to promote the conversion of the phosphorus source into purple phosphorus-based materials. The catalytic effect of the ammonium salt not only reduces the activation energy of the reaction, but also increases the reaction rate, which is beneficial to the conversion of the material;

[0039] S5, cooling and separation: after the reaction is completed, the reaction system is cooled to room temperature, and then the product is separated by centrifugation, filtration, etc.;

[0040] S6. Product purification: The separated purple phosphorus-based material is further purified to remove possible residual ammonium salts and other impurities to ensure the quality of the product.

[0041] The raw materials and reagents used in the specific embodiments of the present invention are all commercially available products.

[0042] In a specific embodiment of the present invention, white phosphorus and red phosphorus are both high-purity phosphorus sources and can be replaced equally without affecting the realization of the technical effects.

[0043] Example 1

[0044] The new and efficient preparation steps of purple phosphorus-based materials are:

[0045] S1. Place 1 g of white phosphorus (WP) and 5 g of ammonium salt (ammonium chloride) in a quartz tube and mix them under an inert atmosphere or vacuum conditions;

[0046] S2. The quartz tube containing white phosphorus and ammonium salt is vacuum sealed 15 cm from the bottom to ensure the airtightness of the reaction;

[0047] S3. Place the vacuum-sealed quartz tube into a muffle furnace, heat it evenly to 475°C at a rate of 5°C / min, and set the pressure to 8 atm. Keep it warm for 12 hours and then naturally cool it to room temperature. Wash it with ethanol and separate the product by centrifugation three times at a speed of 10,000 rpm for 5 minutes. After the centrifugation, filter out the product and dry it to obtain the purple phosphorus-based material.

[0048] Figure 1 This is a schematic diagram of the process flow of Example 1.

[0049] Figure 2 is the XRD pattern of the purple phosphorus-based material prepared in Example 1. Figure 2 It can be seen that purple phosphorus diffraction peaks were observed at 15.28°, 16.33°, 31.58°, and 32.98°, and the corresponding crystal planes were (111), (004), (131), and (008); at the same time, black phosphorus diffraction peaks were observed at 16.87°, 26.60°, 34.16°, 34.97°, and 52.22°, and the corresponding crystal planes were (020), (021), (040), (111), and (060), indicating that the surface sample contained black phosphorus. The results show that purple phosphorus and black phosphorus exist in the material at the same time, and the purple phosphorus-based material is successfully synthesized.

[0050] Figure 3 is the Raman spectrum of the purple phosphorus-based material prepared in Example 1. Figure 3 It can be seen that at 361cm -1 、439cm -1 and 467cm -1 The characteristic peak of violet phosphorus (VP) was observed at 370.7 cm -1 、446.8cm -1 and 475.1cm -1 A of black phosphorus was observed 1 g , B 2 g , A 2 g The characteristic peaks also indicate that black phosphorus (BP) is generated in the material, further confirming the successful preparation of purple phosphorus-based materials.

[0051] Figure 4 The scanning electron microscope images and element distribution diagrams of the purple phosphorus-based material prepared in Example 1, wherein (a), (b) and (c) are SEM images, (d) is an EDS image, (e), (f) and (g) are element distribution images, and (h) is a HR-TEM image. Figure 4It can be seen that (a), (b) and (c) present the scanning electron microscope (SEM) images of the product, respectively, revealing that the material has an irregular layered structure, which is consistent with the morphology of black phosphorus and purple phosphorus; (d) shows the energy dispersive X-ray spectroscopy (EDS) image, which provides intuitive evidence for the quantitative analysis of elemental composition; (e), (f) and (g) depict the distribution of different elements in the material, respectively, and these images clearly map the spatial distribution of the elements; (h) high-magnification transmission electron microscopy (HR-TEM) imaging, the lattice spacing clearly shows the corresponding crystal planes of purple phosphorus and black phosphorus, indicating that the sample is a purple phosphorus-based material. In general, it can be clearly observed that the phosphorus element is very uniformly distributed in the material, indicating a high consistency of the synthesis process. HR-TEM imaging further confirms the presence of typical layered purple phosphorus (VP) morphology and some irregular black phosphorus (BP) morphology in the product.

[0052] Example 2

[0053] Compared with Example 1, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:4, and the specific amounts used are 1 g and 4 g respectively.

[0054] Example 3

[0055] Compared with Example 1, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:3, and the specific amounts used are 1 g and 3 g respectively.

[0056] Example 4

[0057] Compared with Example 1, the only difference is that the temperature is raised to 450°C.

[0058] Example 5

[0059] Compared with Example 4, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:4, and the specific amounts used are 1 g and 4 g respectively.

[0060] Example 6

[0061] Compared with Example 4, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:3, and the specific amounts used are 1 g and 3 g respectively.

[0062] Example 7

[0063] Compared with Example 1, the only difference is that the temperature is raised to 500°C.

[0064] Example 8

[0065] Compared with Example 7, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:4, and the specific amounts used are 1 g and 4 g respectively.

[0066] Example 9

[0067] Compared with Example 7, the only difference is that the mass ratio of white phosphorus to ammonium salt is 1:3, and the specific amounts used are 1 g and 3 g respectively.

[0068] Purple phosphorus-based materials can be prepared by the methods of Examples 2 to 9.

[0069] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. An efficient preparation method of purple phosphorus-based materials, characterized in that the steps include: Using a phosphorus source as a reactant and an ammonium salt as a catalyst, mixing the phosphorus source and the ammonium salt under low oxygen conditions, heating for reaction, and cooling to obtain the purple phosphorus-based material; The phosphorus source is white phosphorus and / or red phosphorus; The ammonium salt is ammonium chloride; The oxygen-poor condition is provided by a vacuum or an inert atmosphere; The temperature of the heating reaction is 450-550°C.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the phosphorus source to the ammonium salt is 1:1-5.

3. The preparation method according to claim 1, characterized in that: The inert atmosphere is an argon atmosphere or a nitrogen atmosphere.

4. The preparation method according to claim 1, characterized in that: The heating reaction has a heating rate of 2-5°C / min, a time of not less than 12h, and a pressure of not less than 5atm.

5. A purple phosphorus-based material obtained by the preparation method according to any one of claims 1 to 4.

6. Application of the purple phosphorus-based material according to claim 5 in the fields of energy, electronics and catalysis.

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