A one-step synthesis of supported Sn 24 P 19.3 Preparation method of I8 catalyst

Abstract

The application relates to the technical field of phosphorus chemical engineering new materials, in particular to a one-step synthesis of a supported Sn 24 P 19.3 I8 catalyst. The application takes a phosphorus source, tin powder, iodine and a carbon additive as raw materials, and a supported Sn 24 P 19.3 I8 catalyst is prepared through one-step solvothermal reaction. The method not only simplifies the preparation process of the catalyst, but also significantly improves the preparation efficiency and scale of the supported Sn 24 P 19.3 I8 catalyst, reduces the energy consumption in the production process, improves the catalytic activity and stability of the catalyst, has important significance for promoting the large-scale and efficient preparation of black phosphorus, lays a catalyst foundation for developing more new elemental phosphorus, and promotes the market promotion and industrialization development of phosphorus chemical engineering new materials.

Description

Technical Field

[0001] The present invention relates to the technical field of new phosphorus chemical materials, in particular to a one-step synthesis of supported Sn 24 P 19.3 Preparation method of I8 catalyst. Background Art

[0002] Black phosphorus is a new stable phosphorus allotrope, in which the phosphorus atoms in the plane are composed of sp 3 The six-membered rings are hybridized and arranged into wrinkled and corrugated shapes. There are strong covalent bonds within the plane, and the layers are connected to each other by van der Waals forces. Thanks to this layered structure, black phosphorus has excellent electron transport performance and tunable optical properties, which makes it have a wide range of application potential in optoelectronic devices, sensors, energy storage materials, biomedicine and other fields. Currently, many methods for preparing black phosphorus have been developed, such as high pressure method, mechanical ball milling method, solvent thermal method, bismuth melting method, mercury reflux method and mineralization method. Among them, the mineralization method is expected to achieve large-scale and efficient preparation of black phosphorus.

[0003] However, the efficient and large-scale preparation of black phosphorus by mineralization is mainly limited by the preparation efficiency and catalytic performance of the catalyst. The main catalyst for the preparation of black phosphorus by mineralization is the P-Sn-I system. A large number of studies have shown that the structure of this ternary complex is Sn 24 P 19.3 I8, using Sn 24 P 19.3 I8 catalyst can significantly improve the preparation efficiency and purity of black phosphorus products by separating the phosphorus source and catalyst. 24 P 19.3 The I8 catalyst method usually uses red phosphorus, tin powder and tin tetraiodide as raw materials, and undergoes a multi-stage temperature rise and fall heat treatment process. This treatment method is energy-intensive and time-consuming, hindering the efficient preparation of the catalyst. Among them, tin tetraiodide is Sn 24 P 19.3 The key precursor materials in the preparation process of I8 are complex, time-consuming, inefficient and have high loss. These problems further lead to the 24 P 19.3 The high preparation cost of I8 catalyst also limits its large-scale production, which in turn hinders the efficient preparation of the catalyst.

[0004] Patent CN113559886A discloses a method for introducing carbon material additives to improve Sn 24 P 19.3 The method for improving the catalytic performance of I8 catalyst, but the method still needs to use SnI4 to prepare Sn 24 P 19.3The I8 catalyst is combined with a carbon additive again for secondary combination, which is time-consuming and inefficient, greatly limits the preparation efficiency of the catalyst, and does not solve the problem of Sn 24 P 19.3 The preparation process of the I8 catalyst is complex, time-consuming, inefficient, and has high loss. Therefore, it is urgent to develop a method for efficiently and high-quality preparation of the supported Sn 24 P 19.3 I8 catalyst. SUMMARY

[0005] The purpose of the present application is to provide a one-step synthesis of a supported Sn 24 P 19.3 I8 catalyst, which uses a phosphorus source, tin powder, iodine and a carbon additive as raw materials, and directly synthesizes a high-purity supported Sn 24 P 19.3 I8 catalyst by one-step solvothermal reaction, so as to solve the problems existing in the prior art and realize efficient, low-cost and large-scale synthesis of the supported catalyst.

[0006] To achieve the above purpose, the present application provides the following solutions:

[0007] One of the technical solutions of the present application: a one-step synthesis of a supported Sn 24 P 19.3 I8 catalyst preparation method, the steps include:

[0008] A phosphorus source, tin powder, iodine and a carbon additive are used as raw materials, and the supported Sn 24 P 19.3 I8 catalyst is prepared by one-step solvothermal reaction.

[0009] The phosphorus source is white phosphorus and / or red phosphorus.

[0010] Further, the carbon additive includes at least one of carbon nanotubes, graphene, graphite, expanded graphite, porous carbon, amorphous carbon, Super P, acetylene black, Ketjen black, reduced graphene oxide and graphene oxide.

[0011] Further, the solvent used in the solvothermal reaction is toluene or xylene.

[0012] Further, the amount of the phosphorus source, tin powder and iodine is prepared according to the element molar ratio in Sn 24 P 19.3 I8.

[0013] Further, the mass ratio of the carbon additive to the sum of the mass of the phosphorus source, tin powder and iodine is 1-5:5.

[0014] Further, the one-step solvothermal reaction prepares the supported Sn24 P 19.3 The steps of the I8 catalyst include:

[0015] dispersing iodine and a carbon auxiliary agent in a solvent to obtain a mixed solution;

[0016] Tin powder and phosphorus source are added to the mixed solution, and the supported Sn is obtained by heat treatment. 24 P 19.3 I8 catalyst.

[0017] Preferably, the heat treatment temperature is 330° C. to 500° C., and the time is not less than 12 hours.

[0018] The present invention directly uses white phosphorus, tin powder, iodine and carbon additives as raw materials, effectively avoiding the existing Sn 24 P 19.3 The complex preparation process and multi-step preparation steps of the supported catalyst caused by the use of tin tetraiodide as raw material in I8 catalyst technology. The one-step solvent thermal preparation method not only shortens the preparation time of the catalyst, reduces the preparation energy consumption and preparation loss, but also improves the preparation efficiency of supported Sn 24 P 19.3 The one-step synthesis method makes the reaction between materials more complete, which is conducive to the formation of stronger bonding between substances, further enhancing the preparation efficiency of supported Sn 24 P 19.3 The catalytic activity and stability of the I8 catalyst are conducive to improving the efficiency of preparing black phosphorus and other new elemental phosphorus.

[0019] The second technical solution of the present invention is to provide a supported Sn prepared by the above preparation method. 24 P 19.3 I8 catalyst.

[0020] The third technical solution of the present invention is to provide a loaded Sn 24 P 19.3 Application of I8 catalyst in improving the efficiency of black phosphorus or purple phosphorus preparation.

[0021] The present invention discloses the following technical effects:

[0022] The method of preparing the catalyst by a one-step solvent thermal reaction not only simplifies the preparation process of the catalyst, but also significantly improves the performance of the supported Sn 24 P 19.3 The preparation efficiency and scale of the I8 catalyst also reduce energy consumption in the production process and improve the catalytic activity and stability of the catalyst. This is of great significance for promoting the large-scale and efficient preparation of black phosphorus, laying the foundation for the development of more new elemental phosphorus catalysts, and promoting the market promotion and industrial development of new phosphorus chemical materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. 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 any creative work.

[0024] Figure 1 Sn 24 P 19.3 XRD pattern of I8 / CNTs;

[0025] Figure 2 Sn 24 P 19.3 Raman pattern of I8 / CNTs;

[0026] Figure 3 Sn 24 P 19.3 SEM images and element distribution maps of I8 / CNTs, where (a) and (b) are SEM images, and (c) to (f) are element distribution maps;

[0027] Figure 4 Sn 24 P 19.3 Transmission electron microscopy images and element distribution maps of I8 / CNTs, where (a) to (c) are transmission electron microscopy images, and (d) to (g) are element distribution maps;

[0028] Figure 5 The supported Sn prepared in Example 1 and Example 2 24 P 19.3 Comparison of XRD spectra of I8 catalyst;

[0029] Figure 6 Sn 24 P 19.3 SEM image and element distribution diagram of I8 / Gr, where (a) is the SEM image, and (b) to (e) are element distribution diagrams;

[0030] Figure 7 Sn 24 P 19.3 Transmission electron microscopy images and element distribution maps of I8 / Gr, where (a) to (d) are transmission electron microscopy images, and (e) to (h) are element distribution maps;

[0031] Figure 8 The supported Sn prepared in Example 3 24 P 19.3 XRD pattern of I8 catalyst;

[0032] Figure 9 Black phosphorus product diagrams and catalyst state change diagrams of the catalysts prepared in Examples 1 to 2 and Comparative Example 1;

[0033] Figure 10 Figure 1 is a diagram of the purple phosphorus product and catalyst state diagram of the catalyst prepared by recycling the catalyst prepared in Example 1, wherein (a) to (c) are state diagrams of the catalyst after the first, second and third uses, respectively, and (d) to (f) are the purple phosphorus products prepared for the first, second and third times, respectively. DETAILED DESCRIPTION

[0034] 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 rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0035] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0036] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice 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 any conflict with any incorporated document, the contents of this specification shall prevail.

[0037] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0038] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0039] The materials and reagents used in the specific embodiments of the present invention are all commercially available products.

[0040] Example 1

[0041] One-step synthesis of supported Sn 24 P 19.3 The steps of I8 catalyst are:

[0042] S1. Weigh 6.825 g of iodine, 19.140 g of tin powder, 4.020 g of white phosphorus, 6.000 g of carbon nanotubes, and 300 mL of toluene and set aside.

[0043] S2. Pour toluene into the quartz liner, add iodine and stir to dissolve, then add carbon nanotubes and stir thoroughly;

[0044] S3, then add tin powder in small amounts and multiple times while stirring, and finally add white phosphorus, and then place it in a stainless steel high-temperature and high-pressure reactor with stirring and seal it;

[0045] S4. Heat the sealed reactor at 330°C for 12 h, cool it to room temperature, and filter and dry it to obtain 34.7 g of supported Sn. 24 P 19.3 I8 catalyst, the conversion rate is 96.38%, denoted as Sn 24 P 19.3 I8 / CNTs.

[0046] Figure 1 Sn 24 P 19.3 The XRD pattern of I8 / CNTs shows that Sn is observed at 29.3°, 30.5°, 33.7°, 41.7° and 49.9°. 24 P 19.3 The diffraction peaks of the I8 catalyst correspond to crystal planes (320), (321), (410), (430) and (600), and the peak at 26.5° corresponds to the (002) crystal plane of carbon nanotubes, indicating that the catalyst was successfully prepared and has high purity and no impurities.

[0047] Figure 2 Sn 24 P 19.3 The Raman graph of I8 / CNTs shows that the -1 The following corresponds to Sn 24 P 19.3 The Raman peak position of I8 is due to the interaction between materials caused by the introduction of carbon nanotubes, which changes the molecular vibration mode and causes Sn 24 P 19.3 The I8 Raman peak shifts. In addition, at 1341 cm -1 and 1594cm -1 The peaks at the bottom correspond to the D and G peaks of carbon nanotubes, further demonstrating the successful preparation of the catalyst.

[0048] Figure 3 Sn 24 P 19.3 SEM and element distribution map of I8 / CNTs, wherein, (a) and (b) are SEM maps, (c)-(f) are element distribution maps, from which it can be seen that Sn 24 P 19.3 I8 is loaded on carbon nanotubes in the form of a sheet, and the distribution of each element is uniform, which is conducive to the high stability of the material in use, and further indicates that the material is successfully synthesized.

[0049] Figure 4 Sn 24 P 19.3 TEM and element distribution map of I8 / CNTs, wherein, (a)-(c) are TEM maps, (d)-(g) are element distribution maps, from which it can be seen that Sn 24 P 19.3 The particle size of I8 is about 150*200 nm, and it is loaded on carbon nanotubes, and the mapping map shows that the distribution of each element is uniform, indicating that the preparation method can successfully load Sn 24 P 19.3 I8 catalyst.

[0050] Example 2

[0051] One-step synthesis of supported Sn 24 P 19.3 The steps of I8 catalyst are:

[0052] S1, weigh 6.825g iodine, 19.140g tin powder, 4.020g white phosphorus, 6.000g graphite (Gr) and 300mL of toluene, and reserve;

[0053] S2, pour toluene into a quartz liner, add iodine and stir to dissolve, then add graphite and stir thoroughly;

[0054] S3, then add tin powder in small amounts and multiple times under stirring, and finally add white phosphorus, then put it into a stainless steel high-temperature and high-pressure reactor with stirring for sealing;

[0055] S4, heat the sealed reactor, and keep it at 330℃ for 12h, then naturally cool to room temperature, and then dry by suction filtration to obtain 35.6g of supported Sn 24 P 19.3 I8 catalyst, the conversion rate is 98.8%, denoted as Sn 24 P 19.3 I8 / Gr.

[0056] Figure 5 The supported Sn prepared in Example 1 and Example 224 P 19.3 The XRD spectrum comparison of I8 catalyst shows that Sn is observed at 29.3°, 30.5°, 33.7°, 41.7° and 49.9°. 24 P 19.3 The diffraction peaks of the I8 catalyst are (320), (321), (410), (430) and (600) for the crystal planes. In addition, the diffraction peak at 26.3° corresponds to the (002) crystal plane of carbon, indicating the successful one-step synthesis of supported Sn on graphite. 24 P 19.3 I8 catalyst.

[0057] Figure 6 Sn 24 P 19.3 SEM image and element distribution diagram of I8 / Gr, where (a) is the SEM image and (b) to (e) are element distribution diagrams. It can be seen from the figure that Sn 24 P 19.3 I8 is loaded on graphite, and the elements are distributed relatively evenly. This morphology and structure is conducive to improving the catalytic stability of the material and indicates that the material has been successfully synthesized.

[0058] Figure 7 Sn 24 P 19.3 Transmission electron microscopy images and element distribution maps of I8 / Gr, where (a) to (d) are transmission electron microscopy images, and (e) to (h) are element distribution maps. It can be seen from the figure that Sn 24 P 19.3 The particle size of I8 is about 1.50 to 2 μm and is supported on graphite. The mapping diagram shows that the elements are evenly distributed, indicating that this preparation method can successfully synthesize supported Sn. 24 P 19.3 I8 catalyst.

[0059] Example 3

[0060] One-step synthesis of supported Sn 24 P 19.3 The steps of I8 catalyst are:

[0061] S1. Weigh 13.650 g of iodine, 38.280 g of tin powder, 8.040 g of white phosphorus, 12.000 g of carbon nanotubes, and 400 mL of toluene and set aside.

[0062] S2. Pour toluene into the quartz liner, add iodine and stir to dissolve, then add carbon nanotubes and stir thoroughly;

[0063] S3, tin powder is added in small amounts for several times under stirring, and white phosphorus is finally added, and then the mixture is put into a stainless steel high-temperature and high-pressure reactor with stirring for sealing;

[0064] S4, the sealed reactor is subjected to heating treatment at 330°C for 12h, and after natural cooling to room temperature, the supported Sn 24 P 19.3 The conversion rate of the I8 catalyst is 98%.

[0065] Figure 8 The supported Sn 24 P 19.3 XRD pattern of the I8 catalyst.

[0066] The conversion rate is still 98% after scale-up, indicating that the method can further realize the preparation of large-scale catalysts.

[0067] XRD characterization results prove that the supported Sn 24 P 19.3 I8 catalyst can still be successfully synthesized at the scale-up, and the catalyst has high purity without impurities.

[0068] Example 4

[0069] One-step synthesis of the supported Sn 24 P 19.3 The steps for preparing the I8 catalyst are as follows:

[0070] S1, 6.825g of iodine, 19.140g of tin powder, 4.020g of white phosphorus, 6.000g of graphene and 300mL of toluene are weighed and prepared;

[0071] S2, toluene is poured into a quartz liner, and iodine is added and stirred to dissolve, and then graphene is added and stirred thoroughly;

[0072] S3, tin powder is added in small amounts for several times under stirring, and white phosphorus is finally added, and then the mixture is put into a stainless steel high-temperature and high-pressure reactor with stirring for sealing;

[0073] S4, the sealed reactor is subjected to heating treatment at 330°C for 12h, and after natural cooling to room temperature, the supported Sn 24 P 19.3 I8 catalyst.

[0074] Example 5

[0075] One-step synthesis of the supported Sn 24 P 19.3 The steps for preparing the I8 catalyst are as follows:

[0076] S1. Weigh 6.825 g of iodine, 19.140 g of tin powder, 4.020 g of white phosphorus, 6.000 g of porous carbon, and 300 mL of toluene and set aside.

[0077] S2. Pour toluene into the quartz liner, add iodine and stir to dissolve, then add porous carbon and stir thoroughly;

[0078] S3, then add tin powder in small amounts and multiple times while stirring, and finally add white phosphorus, and then place it in a stainless steel high-temperature and high-pressure reactor with stirring and seal it;

[0079] S4, heat the sealed reactor at 330 ° C for 12 hours, cool it to room temperature naturally, and filter and dry it to obtain the supported Sn 24 P 19.3 I8 catalyst.

[0080] Comparative Example 1

[0081] First, tin tetraiodide is prepared, and then Sn is further prepared. 24 P 19.3 I8 catalyst, then Sn 24 P 19.3 The I8 catalyst and carbon promoter are further compounded in the following steps:

[0082] S1. Weigh 16.0 g of iodine and 4.8 g of tin into a round-bottom flask, then add 70-100 mL of toluene.

[0083] S2. Build a condensation reflux apparatus and heat the round-bottom flask in an oil bath to 115°C to allow toluene to evaporate, condense, and reflux continuously until the toluene solution changes from purple-red to orange-red. The entire reaction process takes 3 hours. After the reaction is complete, the iodine-containing toluene solution will be converted into a toluene solution containing tin tetraiodide.

[0084] S3, set up a filtration device, and after the reaction is completed, perform hot filtration on the toluene solution containing tin tetraiodide to separate the unreacted tin powder;

[0085] S4. Place the filtered toluene solution in a beaker and place it in a fume hood. After the toluene is completely evaporated, tin tetraiodide crystals are obtained.

[0086] S5. Weigh 4.08 g of red phosphorus, 7.51 g of tin tetraiodide, and 15.66 g of tin powder respectively, and grind them in a mortar to reduce the particle size while achieving uniform mixing of the raw materials;

[0087] S6. Divide the ground powder into two parts and seal them in two vacuum quartz tubes (quartz tube inner diameter 18 mm, wall thickness 2 mm, sealed at a length of 120 mm);

[0088] S7. Place the quartz tube in a muffle furnace for reaction. First, raise the temperature from room temperature to 550°C at a rate of 5°C / min, keep it at 550°C for 30 minutes, then cool it to 500°C within 225 minutes and keep it at that temperature for 30 minutes. After keeping it at that temperature, raise it to 550°C within 10 minutes. This process is repeated 7 times before terminating the program and cooling it naturally to room temperature.

[0089] S8. After the reaction is completed, take out the tin iodide-phosphorus block in the quartz tube, grind it into powder and sieve it to 200 mesh to obtain Sn 24 P 19.3 I8 catalyst powder;

[0090] S9, Sn with a mass ratio of 0.4:0.6 24 P 19.3 I8 and graphite are mixed and ground evenly;

[0091] S10, then put the evenly ground mixture into a rectangular mold and press it to 5MPa and keep it for 30min, and then release the pressure to obtain a rectangular Sn containing graphite additive. 24 P 19.3 I8 catalyst;

[0092] S11, Sn containing graphite additive 24 P 19.3 I8 catalyst was broken into pieces and sieved with a 5-8 mesh sieve to obtain granular Sn containing graphite additive. 24 P 19.3 I8 catalyst.

[0093] Test example

[0094] The catalysts prepared in Example 1, Example 2 and Comparative Example 1 were used to catalyze the preparation of black phosphorus in the following manner:

[0095] S1. The quantitative amount of the phosphorus source for the reaction is 50 g of red phosphorus per portion, and the quantitative amount of the three groups of catalysts in Example 1, Example 2 and Comparative Example 1 is 5 g per portion.

[0096] S2. A quartz tube (33mm inner diameter, 37mm outer diameter, 150mm length) was selected as the inner lining. The red phosphorus raw material was placed at the high-temperature end, the catalyst was placed near the red phosphorus raw material end, and black phosphorus / purple phosphorus was generated at the low-temperature end. The red phosphorus, catalyst, and generated black phosphorus / purple phosphorus were separated by nickel foam.

[0097] S3. Place the quartz lining in a stainless steel reactor and heat treat in a dual-zone tubular furnace (black phosphorus preparation temperature: high end temperature 500°C, low end temperature 480°C; purple phosphorus preparation temperature: high end temperature 560°C, low end temperature 540°C) to produce purple phosphorus. After the reaction is completed, cool naturally to room temperature to obtain the black phosphorus / purple phosphorus product.

[0098] Figure 9 The black phosphorus product diagram and catalyst state change diagram of the catalysts prepared in Examples 1-2 and Comparative Example 1 show that the catalysts prepared in Examples 1-2 of the present invention have higher catalytic activity, and the yield of preparing black phosphorus reaches more than 95%, while the catalyst prepared in Comparative Example 1 has a black phosphorus conversion rate of about 90%. Comparing the states of the three groups of catalysts after catalytic preparation of black phosphorus, it is observed that the supported Sn prepared in Examples 1 and 2 has a higher catalytic activity than that in Comparative Example 1. 24 P 19.3 The I8 catalyst did not show any sintering phenomenon; while the Sn 24 P 19.3 The I8 catalyst is in a sintered state. This result shows that the one-step solvent thermal method of the present invention can prepare supported Sn 24 P 19.3 I8 catalyst has high catalytic activity and thermal stability in the preparation of black phosphorus, which is due to the Sn 24 P 19.3 A stronger bond is formed between I8 and the auxiliary agent, and the tablet preparation method has stronger stability compared with the physical mixing and tableting method of Comparative Example 1.

[0099] Figure 10 The purple phosphorus product diagram and catalyst state diagram of the catalyst prepared by recycling the catalyst prepared in Example 1, wherein (a) to (c) are the state diagrams of the catalyst after the first, second and third use, respectively, and (d) to (f) are the purple phosphorus products prepared for the first, second and third use, respectively. As can be seen from the figure, the catalyst prepared in Example 1 of the present invention has high catalytic activity and stability. It can still produce purple phosphorus after being reused three times, indicating that the supported Sn 24 P 19.3 I8 catalyst has high catalytic activity. Since the preparation temperature of purple phosphorus is much higher than that of black phosphorus, it can be seen from the figure that the supported Sn prepared by the present invention 24 P 19.3 After the I8 catalyst was used to prepare purple phosphorus at high temperature, the catalyst remained fluffy and no sintering occurred, indicating that the supported Sn 24 P 19.3 I8 catalyst has higher stability.

[0100] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. One-step synthesis of supported Sn 24 P 19.3 The preparation method of I8 catalyst is characterized in that the steps include: The supported Sn is prepared by a one-step solvent thermal reaction using phosphorus source, tin powder, iodine and carbon additive as raw materials. 24 P 19.3 I8 catalyst; The phosphorus source is white phosphorus and / or red phosphorus; The solvent used in the solvothermal reaction is toluene or xylene; The temperature of the solvent thermal reaction is 330° C. and the time is not less than 12 hours.

2. The preparation method according to claim 1, wherein The carbon additive includes at least one of carbon nanotubes, graphene, graphite, expanded graphite, porous carbon, amorphous carbon, Super P, acetylene black, Ketjen black, reduced graphene oxide and graphene oxide.

3. The preparation method according to claim 1, wherein The amount of the phosphorus source, tin powder and iodine is based on Sn 24 P 19.3 The molar ratio of elements in I8 is prepared.

4. The preparation method according to claim 1, wherein The mass ratio of the carbon additive to the sum of the mass of the phosphorus source, the tin powder and the iodine is 1-5:

5.

5. The preparation method according to claim 1, wherein The one-step solvent thermal reaction prepares the supported Sn 24 P 19.3 The steps of the I8 catalyst include: dispersing iodine and a carbon auxiliary agent in a solvent to obtain a mixed solution; Tin powder and phosphorus source are added to the mixed solution, and the supported Sn is obtained by heat treatment. 24 P 19.3 I8 catalyst.

6. The supported Sn prepared by the preparation method according to claim 1 24 P 19.3 I8 catalyst.

7. The supported Sn as claimed in claim 6 24 P 19.3 Application of I8 catalyst in improving the efficiency of black phosphorus or purple phosphorus preparation.

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