Preparation method for one-step synthesis of supported Sn24P19.3I8 catalyst

Abstract

The invention relates to the technical field of phosphorus chemical new materials, in particular to a preparation method for synthesizing a supported Sn24P19.3I8 catalyst in one step. According to the method, the phosphorus source, the tin powder, the iodine and the carbon additive are used as raw materials, and the supported Sn24P19.3I8 catalyst is prepared through one-step solvothermal reaction, so that the preparation process of the catalyst is simplified, the preparation efficiency and scale of the supported Sn24P19.3I8 catalyst are remarkably improved, meanwhile, the energy consumption in the production process is reduced, the catalytic activity and stability of the catalyst are improved, and the method is suitable for industrial production. The method has important significance for promoting large-scale efficient preparation of black phosphorus, lays a catalyst foundation for developing more novel elemental phosphorus, and promotes market promotion and industrial development of phosphorus chemical new materials.

Description

Technical Field

[0001] The present invention relates to the technical field of new phosphorus chemical materials, and 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. 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. At present, many methods for preparing black phosphorus have been developed, such as high pressure method, mechanical ball milling method, solvothermal 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 the 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 heating and cooling process. This treatment method is energy-intensive and time-consuming, which hinders 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 have complex preparation processes, long time consumption, low efficiency and 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 of introducing carbon material additives to increase Sn 24 P 19.3 I8 catalyst, but this method still needs to use SnI4 to prepare Sn 24 P 19.3I8 catalyst, and then combined with carbon additive for secondary preparation, the preparation is time-consuming and inefficient, which greatly limits the preparation efficiency of the catalyst and does not solve the problem of Sn 24 P 19.3 The preparation process of I8 catalyst is complex, time-consuming, inefficient and has high loss. Therefore, it is urgent to develop a method for preparing supported Sn with high efficiency and high quality. 24 P 19.3 I8 Catalyst method. Summary of the invention

[0005] The purpose of the present invention is to provide a one-step synthesis of supported Sn 24 P 19.3 The preparation method of I8 catalyst uses phosphorus source, tin powder, iodine and carbon additive as raw materials, and directly synthesizes high-purity supported Sn through a one-step solvent thermal reaction. 24 P 19.3 I8 catalyst is used to solve the problems existing in the above-mentioned prior art and realize the efficient, low-cost and large-scale synthesis of supported catalysts.

[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 a one-step synthesis of supported Sn 24 P 19.3 The preparation method of I8 catalyst comprises the following steps:

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

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

[0010] Furthermore, 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] Furthermore, the solvent used in the solvothermal reaction is toluene or xylene.

[0012] Furthermore, the amount of the phosphorus source, tin powder and iodine is based on Sn 24 P 19.3 The molar ratio of the elements in I8 is used for preparation.

[0013] Furthermore, 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 to 5:5.

[0014] Furthermore, the one-step solvothermal reaction prepares the supported Sn24 P 19.3 The steps of 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 the 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 preparation efficiency of 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 load-type Sn 24 P 19.3 Application of I8 catalyst in improving the preparation efficiency of black phosphorus or purple phosphorus.

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

[0022] The method for 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 the 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 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.

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

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

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

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

[0028] Figure 5 The supported Sn prepared in Example 1 and Example 2 24 P 19.3 XRD spectrum comparison 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] Fig. 9 The black phosphorus product diagram and catalyst state change diagram of the catalyst prepared by the catalytic preparation of Examples 1 to 2 and Comparative Example 1;

[0033] Fig.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 state diagrams of the catalyst after the first, second and third uses, respectively, and (d) to (f) are 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 should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0035] 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.

[0036] 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.

[0037] 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.

[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 iodine, 19.140 g tin powder, 4.020 g white phosphorus, 6.000 g carbon nanotubes and 300 mL toluene for later use;

[0043] S2, pouring toluene into the quartz liner, adding iodine and stirring to dissolve, and then adding carbon nanotubes and stirring thoroughly;

[0044] S3, adding tin powder in small amounts and multiple times under stirring, and finally adding white phosphorus, followed by placing in a stainless steel high-temperature and high-pressure reactor with stirring and sealing;

[0045] S4. The sealed reactor was heated at 330°C for 12 h, cooled naturally to room temperature, and filtered and dried 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 XRD pattern of I8 / CNTs. It can be seen from the figure that Sn was 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 the carbon nanotubes, indicating that the catalyst was successfully prepared and has a high purity and is free of impurities.

[0047] Figure 2 Sn 24 P 19.3 Raman graph of I8 / CNTs. It can be seen from the figure that at 500cm -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 1341cm -1 and 1594cm -1 The peaks at the bottom correspond to the D and G peaks of carbon nanotubes, further illustrating the successful preparation of the catalyst.

[0048] Figure 3 Sn 24 P 19.3 SEM images and element distribution diagrams of I8 / CNTs, where (a) and (b) are SEM images, and (c) to (f) are element distribution diagrams. It can be seen from the figure that Sn 24 P 19.3 I8 is loaded on carbon nanotubes in the form of sheets, and the distribution of various elements is relatively uniform, which is conducive to the material having higher stability when used, and also further indicates that the material was successfully synthesized.

[0049] Figure 4 Sn 24 P 19.3 Transmission electron microscopy images and element distribution diagrams of I8 / CNTs, where (a) to (c) are transmission electron microscopy images, and (d) to (g) are element distribution diagrams. It can be seen from the figure that Sn 24 P 19.3 The particle size of I8 is about 150*200nm, and it is loaded on carbon nanotubes. The mapping diagram shows that the elements are evenly distributed, 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 6.825 g iodine, 19.140 g tin powder, 4.020 g white phosphorus, 6.000 g graphite (Gr) and 300 mL toluene for later use;

[0053] S2. Pour toluene into the quartz lining, add iodine and stir to dissolve, then add graphite and stir thoroughly;

[0054] S3, adding tin powder in small amounts and multiple times under stirring, and finally adding white phosphorus, followed by placing in a stainless steel high-temperature and high-pressure reactor with stirring and sealing;

[0055] S4. The sealed reactor was heated at 330°C for 12 h, cooled naturally to room temperature, and filtered and dried to obtain 35.6 g 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, (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 distribution of various elements is relatively uniform. 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 diagrams of I8 / Gr, where (a) to (d) are transmission electron microscopy images, and (e) to (h) are element distribution diagrams. It can be seen from the figure that Sn 24 P 19.3 The particle size of I8 is about 1.50-2 μm and is loaded on graphite. The mapping diagram shows that the elements are evenly distributed, indicating that this preparation method can successfully synthesize loaded 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 iodine, 38.280 g tin powder, 8.040 g white phosphorus, 12.000 g carbon nanotubes and 400 mL toluene for later use;

[0062] S2, pouring toluene into the quartz liner, adding iodine and stirring to dissolve, and then adding carbon nanotubes and stirring thoroughly;

[0063] S3, adding tin powder in small amounts and multiple times under stirring, and finally adding white phosphorus, followed by placing in a stainless steel high-temperature and high-pressure reactor with stirring and sealing;

[0064] S4, heat the sealed reactor at 330°C for 12 h, cool it naturally to room temperature, and then filter and dry to obtain 70.6 g of supported Sn 24 P 19.3 I8 catalyst, the conversion rate is 98%.

[0065] Figure 8 The supported Sn prepared in Example 3 24 P 19.3 XRD pattern of I8 catalyst.

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

[0067] XRD characterization results show that the supported Sn can still be successfully synthesized under this scale-up. 24 P 19.3 I8 catalyst, and the catalyst has high purity and no impurities.

[0068] Example 4

[0069] One-step synthesis of supported Sn 24 P 19.3 The steps of I8 catalyst are:

[0070] S1. Weigh 6.825 g iodine, 19.140 g tin powder, 4.020 g white phosphorus, 6.000 g graphene and 300 mL toluene for later use;

[0071] S2, pouring toluene into the quartz lining, adding iodine and stirring to dissolve, and then adding graphene and stirring thoroughly;

[0072] S3, adding tin powder in small amounts and multiple times under stirring, and finally adding white phosphorus, followed by placing in a stainless steel high-temperature and high-pressure reactor with stirring and sealing;

[0073] S4, heat the sealed reactor at 330 ° C for 12 hours, cool it to room temperature naturally, and then filter and dry it to obtain the supported Sn 24 P 19.3 I8 catalyst.

[0074] Example 5

[0075] One-step synthesis of supported Sn 24 P 19.3 The steps of I8 catalyst are:

[0076] S1. Weigh 6.825 g iodine, 19.140 g tin powder, 4.020 g white phosphorus, 6.000 g porous carbon and 300 mL toluene for later use;

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

[0078] S3, adding tin powder in small amounts and multiple times under stirring, and finally adding white phosphorus, followed by placing in a stainless steel high-temperature and high-pressure reactor with stirring and sealing;

[0079] S4, heat the sealed reactor at 330 ° C for 12 hours, cool it to room temperature naturally, and then 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, and then Sn 24 P 19.3 The I8 catalyst and the carbon additive are further compounded, and the specific steps are as follows:

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

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

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

[0085] S4, placing the filtered toluene solution in a beaker and placing it in a fume hood, and obtaining tin tetraiodide crystals after the toluene is completely evaporated;

[0086] S5, weighing 4.08g of red phosphorus, 7.51g of tin tetraiodide and 15.66g of tin powder respectively, and grinding 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 (the inner diameter of the quartz tube is 18 mm, the wall thickness is 2 mm, and the tube is sealed at a length of 120 mm);

[0088] S7, placing the quartz tube in a muffle furnace for reaction, firstly raising the temperature from room temperature to 550°C at a rate of 5°C / min, keeping the temperature at 550°C for 30min, then cooling to 500°C within 225min and keeping the temperature for 30min, and then raising the temperature to 550°C within 10min after keeping the temperature, and the process is repeated 7 times before terminating the program and cooling naturally to room temperature;

[0089] S8. After the reaction is completed, take out the tin iodide phosphate block in the quartz tube, grind it into powder and sieve it to 200 mesh powder 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 pressurize it to 5MPa and keep it for 30min, and then release the pressure to obtain a rectangular Sn containing graphite additives. 24 P 19.3 I8 catalyst;

[0092] S11, Sn containing graphite additive 24 P 19.3 The I8 catalyst was crushed 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, select a quartz tube as the inner lining (quartz tube inner diameter 33mm, outer diameter 37mm, length 150mm), place the red phosphorus raw material at the high temperature end, place the catalyst near the end of the red phosphorus raw material, and generate black phosphorus / purple phosphorus at the low temperature end. The red phosphorus, the catalyst and the generated black phosphorus / purple phosphorus are separated by nickel foam.

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

[0098] Fig. 9 The black phosphorus product diagram and catalyst state change diagram of the catalyst prepared by Examples 1-2 and Comparative Example 1. It can be seen from the figure that the catalyst prepared by Examples 1-2 of the present invention has a higher catalytic activity, and the yield of preparing black phosphorus reaches more than 95%, while the catalyst prepared by Comparative Example 1 prepares black phosphorus, and the conversion rate of black phosphorus is 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 by Examples 1 and 2 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 solvothermal 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 tablet preparation method of Comparative Example 1.

[0099] Fig.10 The purple phosphorus product diagram and catalyst state diagram of the catalyst prepared in Example 1 after the catalyst is recycled, 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 in 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, and can still prepare 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 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. 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 solvothermal reaction using a phosphorus source, tin powder, iodine and a carbon additive as raw materials. 24 P 19.3 I8 catalyst; The phosphorus source is white phosphorus and / or red phosphorus.

2. The preparation method according to claim 1, characterized in that 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; the solvent used in the solvothermal reaction is toluene or xylene.

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

4. The preparation method according to claim 1, characterized in that: The mass ratio of the carbon auxiliary agent to the sum of the mass of the phosphorus source, the tin powder and the iodine is 1 to 5:

5.

5. The preparation method according to claim 1, characterized in that: The one-step solvothermal reaction prepares the supported Sn 24 P 19.3 The steps of 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 preparation method according to claim 5, characterized in that: The temperature of the heat treatment is 330° C. to 500° C., and the time is not less than 12 hours.

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

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

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