A method for synchronously preparing one-dimensional and two-dimensional Hittorf purple phosphorus nanomaterials

Abstract

The present application relates to a kind of methods for synchronously preparing one-dimensional and two-dimensional Hittorf purple phosphorus nanomaterials, with different purity amorphous red phosphorus as raw material, first by iodine vapor transport method on double-temperature zone tube furnace, crystal Hittorf purple phosphorus is grown, then by conventional liquid phase stripping and syrup ball milling stripping technology, one-dimensional, two-dimensional nanomaterials of Hittorf purple phosphorus nanobelt and nanosheet are synchronously prepared.The prepared Hittorf purple phosphorus nanomaterial, band gap width range is 1.80-2.5 eV, can be used for photoelectric detector, photocatalytic hydrogen production and carbon dioxide reduction and organic degradation, also can be applied to lithium ion battery negative electrode, with great application prospect.At the same time, the preparation method of the present application is simple, and the manufacturing cost is low, which is beneficial to large-scale preparation.

Description

Technical Field

[0001] This invention relates to a method for simultaneously preparing one-dimensional and two-dimensional Hittorf purple phosphorene nanomaterials, which has important application prospects in photoelectric detection and belongs to the fields of nanomaterials and optical, electronic and semiconductor material preparation technology. Background Technology

[0002] Hittorf phosphorus is a one-dimensional and two-dimensional nanomaterial derived from Hittorf phosphorus, possessing a unique crystal structure and excellent photoelectric properties. As an allotrope of phosphorus, Hittorf phosphorus exhibits great potential in photoelectric detection, photocatalysis, and energy storage due to its high stability and wide band gap (approximately 1.80-2.0 eV), particularly in photocatalytic hydrogen production, carbon dioxide reduction, organic matter degradation, and as a negative electrode material for lithium-ion batteries. Compared to other phosphorus-based two-dimensional materials such as black phosphorus, Hittorf phosphorus not only possesses superior chemical stability but also allows for the controllable growth of one-dimensional and two-dimensional nanostructures through reasonable preparation methods.

[0003] Currently, the preparation of Hittorf phosphorus mainly relies on the growth and exfoliation techniques of Hittorf phosphorus. Obtaining one-dimensional and two-dimensional nanostructured Hittorf phosphorus requires different Hittorf phosphorus synthesis methods and exfoliation techniques, which undoubtedly increases production costs. Therefore, developing an efficient, low-cost, and morphology-controllable method for preparing Hittorf phosphorus, and being able to obtain one-dimensional nanoribbons and two-dimensional nanosheets of Hittorf phosphorus using only different exfoliation techniques, is a current research challenge.

[0004] To address the aforementioned problems, this invention proposes a method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials. Summary of the Invention

[0005] This invention proposes a method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanoribbons and nanosheets using an iodine vapor transport method combined with liquid-phase exfoliation and syrup ball milling exfoliation. First, high-quality Hittorf phosphorus crystals are grown in a dual-temperature zone tube furnace using amorphous red phosphorus of varying purities via iodine vapor transport. Then, Hittorf phosphorus nanoribbons are prepared using conventional liquid-phase exfoliation, and Hittorf phosphorus nanosheets are prepared using syrup ball milling exfoliation. The one-dimensional and two-dimensional Hittorf phosphorus nanomaterials exhibit wide band gaps, regular morphology, and excellent performance, making them widely applicable in photodetectors, photocatalysis, and energy storage devices. Compared with existing technologies, this invention's preparation method offers advantages such as simple process, low cost, and suitability for large-scale production, providing technical support and material assurance for the practical application of Hittorf phosphorus.

[0006] This invention provides a method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials, characterized by comprising the following steps:

[0007] (1) Amorphous red phosphorus and iodine are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0008] (2) Preparation of Hittorf purple phosphorus by iodine vapor transport method: The quartz tube containing amorphous red phosphorus and iodine in (1) was placed in a horizontal dual-temperature zone tube furnace. The two ends of the quartz tube were placed in the heating zone of the dual-temperature zone tube furnace, and the side without the reagent was raised so that it was at a certain angle to the direction of the tube of the tube furnace. The temperature of the dual temperature zone was set as follows: the temperature of the side containing amorphous red phosphorus and iodine was set as follows: the temperature was raised from room temperature to 460-510℃ at a certain heating rate and held for 20-25 h, and then cooled to room temperature at a certain cooling rate. The temperature of the side without the reagent was set as follows: the temperature was raised from room temperature to 440-460℃ at the same heating time as the reagent zone and held for the same time, and then cooled to room temperature at the same cooling time as the reagent zone. After the reaction was completed, the quartz tube was broken and the plate-like crystalline purple phosphorus product on the tube wall was peeled off with tweezers.

[0009] (3) Disperse the flaky crystalline phosphine product obtained in (2) in a solvent and sonicate it in a cell disruptor or ultrasonic cleaner for 1-8 h. Keep the temperature of the dispersion constant below 30℃ during the sonication process. Centrifuge the ultrasonically treated dispersion at a speed of 5000 rpm or higher to remove the unpeeled precipitate. After obtaining the supernatant, centrifuge the supernatant at a speed of 10000 rpm or higher, collect the precipitate, and dry it in a vacuum drying oven to obtain one-dimensional Hittorf phosphine nanoribbon powder.

[0010] (4) Grind the Hittorf phosphorus flake crystals prepared in (2) into powder using a mortar and pestle, then mix them with glucose syrup solution in a certain proportion and place them in a ball mill jar. Weigh a certain amount of grinding balls with diameters of 10 mm and 2 mm and place them in the ball mill jar. Place the ball mill jar and another ball mill jar of the same mass on a ball mill for ball milling. After ball milling, wash the slurry mixture in the ball mill jar with deionized water and remove the filtrate by filtration through a microporous membrane. Repeat the washing-filtration process three times or more to remove the glucose syrup. Finally, disperse the product filtered through the microporous membrane in deionized water and uniformly disperse it for 10-30 min using an ultrasonic cleaner. Then, centrifuge the dispersion at a speed of 1000 rpm or higher, collect the supernatant, freeze the supernatant in a refrigerator to form ice cubes, and then freeze-dry the ice cubes in a freeze dryer to obtain Hittorf phosphorus nanosheets.

[0011] The method for simultaneously preparing one-dimensional and two-dimensional Hittorf purple phosphorus nanomaterials is characterized in that, in step (1), the purity of amorphous red phosphorus is 90%-99.9999%, the purity of elemental iodine is 99.0%-99.9%, the mass ratio of amorphous red phosphorus to elemental iodine is 10:1-30:1, and the vacuum degree of the vacuum seal is <10. -4 Pa.

[0012] The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials is characterized in that, in step (2), the quartz tube placed in the heating zone of a horizontal dual-temperature zone tube furnace has its side without reagents raised at an angle of 5-60° to the direction of the furnace tube; the dual-temperature zone heating is set as follows: the side containing amorphous red phosphorus and iodine reagents is heated from room temperature to 460-510°C at a heating rate of 1-5°C / min and held for 20-25 h, then cooled to room temperature at a cooling rate of 1-5°C / min; the temperature of the side without reagents is set as follows: the side with reagents is heated from room temperature to 440-460°C for the same heating time as the side with reagents and held for the same time, then cooled to room temperature for the same cooling time as the side with reagents. The temperature at both ends of the heated quartz tube is always 20-50°C lower on the side without reagents than on the side with reagents.

[0013] The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials is characterized in that, in step (3), the solvents used are deionized water, anhydrous ethanol, isopropanol, N-methylpyrrolidone, and N,N-dimethylformamide, with the amount of solvent added being 10-50 mg of crystalline phosphorus per milliliter of solvent; the ultrasonic time is 1-8 h, and the ultrasonic power is 120-2000 W; the temperature of the dispersion is kept constant at 3-30℃ during the ultrasonic process. The ultrasonically treated dispersion is centrifuged at a speed of 5000-10000 rpm.

[0014] The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials is characterized in that, in step (4), the concentration of the glucose syrup solution is 20wt%-60wt%; the amount of glucose syrup solution and crystalline phosphorus is 0.1-0.5 g of crystalline phosphorus per 5 ml of glucose syrup solution; the amount of grinding balls is 10-20 g of grinding balls per 0.1 g of crystalline phosphorus, with 20%-30% of the grinding balls having a diameter of 10 mm and 70%-80% having a diameter of 2 mm; the operating parameters of the ball mill are set as follows: rotation speed 500-800 rpm, forward rotation for 20-60 min, reverse rotation for 20-60 min, interval 30-60 s, continuous ball milling for 12-48 h; after ball milling, the slurry mixture in the ball milling tank is poured out and washed with deionized water, and the filtrate is removed by filtration through a microporous filter membrane. The mixture is washed and filtered repeatedly 3-6 times to remove the glucose syrup. The product after removing glucose syrup was dispersed in deionized water and uniformly dispersed for 10-30 min using an ultrasonic cleaner. The dispersion was then centrifuged at 1000-8000 rpm, and the supernatant was collected and freeze-dried to obtain Hittorf purple phosphorus nanosheets. Attached Figure Description

[0015] Figure 1 Scanning electron microscope image of purple phosphorene nanoribbon powder;

[0016] Figure 2 This is a scanning electron microscope image of purple phosphorene nanosheet powder;

[0017] Figure 3 Energy-absorption curves of flaky crystalline purple phosphorus powder prepared by the iodine vapor transport method, obtained by the Tauc plot method;

[0018] Figure 4 Energy-absorption curves of phosphane nanoribbons / nanofa sheets obtained by Tauc plot method. Detailed Implementation

[0019] The following is a further description of the invention, but not a limitation thereof. Example 1

[0020] (1) 1 g of high-purity amorphous red phosphorus with a purity of 99.99% and 50 mg of iodine with a purity of 99.9% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0021] (2) 1 g of commercially available amorphous red phosphorus with a purity of 90% and 50 mg of iodine with a purity of 99.9% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0022] (3) Preparation of Hittorf purple phosphorus by iodine vapor transport method: Quartz tubes containing amorphous red phosphorus and iodine as described in (1) and (2) were placed in a horizontal dual-temperature zone tube furnace. Both ends of the quartz tubes were placed in the heating zone of the dual-temperature zone tube furnace, and the side without reagents was raised so that it was at a 5° angle to the direction of the tube furnace tube. The temperature of the dual temperature zones was set as follows: the temperature of the side containing amorphous red phosphorus and iodine was set to rise from room temperature to 460°C at a heating rate of 1°C / min and hold for 20 h, and then cool down to room temperature at a cooling rate of 1°C / min; the temperature of the side without reagents was set to rise from room temperature to 440°C for the same heating time as the reagent-containing zone and hold for the same time, and then cool down to room temperature for the same cooling time as the reagent-containing zone. After the reaction was completed, the quartz tubes were broken, and the flaky crystalline purple phosphorus product on the tube wall was peeled off with tweezers.

[0023] (4) The flaky crystalline phosphine product obtained in (3) was dispersed in anhydrous ethanol and sonicated for 4 h in a cell disruptor or ultrasonic cleaner. The temperature of the dispersion was kept constant below 30°C during the sonication process. The dispersion after ultrasonic treatment was centrifuged at 5000 rpm to remove the unpeeled precipitate and obtain the supernatant. The supernatant was then centrifuged at 10000 rpm to collect the precipitate and dried in a vacuum drying oven to obtain one-dimensional Hittorf phosphine nanoribbon powder.

[0024] (5) The Hittorf phosphorus flake crystals prepared by the iodine vapor transport method in (2) in (3) are ground into powder using a mortar and pestle. Then, they are mixed with glucose syrup solution in a certain proportion and placed in a ball mill jar. A certain amount of grinding balls with diameters of 10 mm and 2 mm are weighed and placed in the ball mill jar. The ball mill jar and another ball mill jar of the same mass are placed on a ball mill for ball milling. After ball milling, the slurry mixture in the ball mill jar is washed with deionized water and the filtrate is removed by vacuum filtration through a microporous membrane. The mixture is washed and vacuum filtered three times or more to remove the glucose syrup. Finally, the product after vacuum filtration on the microporous membrane is dispersed in deionized water and uniformly dispersed for 10 min using an ultrasonic cleaner. The dispersion is then centrifuged at 1000 rpm in a centrifuge. The supernatant is collected and frozen in a refrigerator. The ice cubes are then freeze-dried in a freeze dryer to obtain Hittorf phosphorus nanosheets. Example 2

[0025] (1) 1g of high-purity amorphous red phosphorus with a purity of 99.999% and 40mg of iodine with a purity of 99.5% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0026] (2) 1g of commercially available amorphous red phosphorus with a purity of 99.5% and 40mg of iodine with a purity of 99.5% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0027] (3) Preparation of Hittorf purple phosphorus by iodine vapor transport method: Quartz tubes containing amorphous red phosphorus and iodine as described in (1) and (2) were placed in a horizontal dual-temperature zone tube furnace. Both ends of the quartz tubes were placed in the heating zone of the dual-temperature zone tube furnace, and the side without reagents was raised so that it was at a 10° angle to the direction of the tube of the furnace. The temperature of the dual-temperature zone was set as follows: the temperature of the side containing amorphous red phosphorus and iodine was set to rise from room temperature to 480°C at a heating rate of 2°C / min and hold for 22 h, and then cool down to room temperature at a cooling rate of 2°C / min; the temperature of the side without reagents was set to rise from room temperature to 450°C for the same heating time as the reagent-containing zone and hold for the same time, and then cool down to room temperature for the same cooling time as the reagent-containing zone. After the reaction was completed, the quartz tubes were broken, and the flaky crystalline purple phosphorus product on the tube wall was peeled off with tweezers.

[0028] (4) The flaky crystalline pheophyte product obtained in (3) was dispersed in deionized water and sonicated for 6 h in a cell disruptor or ultrasonic cleaner. The temperature of the dispersion was kept constant below 30 °C during sonication. The ultrasonically treated dispersion was centrifuged at 8000 rpm to remove unremoved precipitate. The supernatant was then centrifuged at 10000 rpm to collect the precipitate, which was then dried in a vacuum drying oven to obtain one-dimensional Hittorf pheophyte nanoribbon powder, such as... Figure 1 As shown.

[0029] (5) Grind the Hittorf purple phosphorus flake crystals prepared by the iodine vapor transport method in (2) into powder using a mortar and pestle. Then mix them with glucose syrup solution in a certain proportion and put them into a ball mill jar. Weigh a certain amount of grinding balls with diameters of 10 mm and 2 mm and put them into the ball mill jar. Place the ball mill jar and another ball mill jar of the same mass on a ball mill for ball milling. After ball milling, wash the slurry mixture in the ball mill jar with deionized water and remove the filtrate by filtration through a microporous membrane. Repeat the washing-filtration process three times or more to remove the glucose syrup. Finally, disperse the product after filtration on the microporous membrane in deionized water and disperse it evenly for 20 min using an ultrasonic cleaner. Then place the dispersion in a centrifuge at a speed of 3000 rpm, collect the supernatant, freeze the supernatant in a refrigerator to make ice cubes, and then freeze-dry the ice cubes in a freeze dryer to obtain Hittorf purple phosphorus nanosheets, such as Figure 2 As shown. Example 3

[0030] (1) 1g of high-purity amorphous red phosphorus with a purity of 99.9999% and 67mg of iodine with a purity of 99.0% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0031] (2) 1g of commercially available amorphous red phosphorus with a purity of 99.9% and 67mg of iodine with a purity of 99.0% are vacuum sealed in a quartz glass tube and concentrated on one side of the bottom.

[0032] (3) Preparation of Hittorf purple phosphorus by iodine vapor transport method: Quartz tubes containing amorphous red phosphorus and iodine as described in (1) and (2) were placed in a horizontal dual-temperature zone tube furnace. Both ends of the quartz tubes were placed in the heating zone of the dual-temperature zone tube furnace, and the side without reagents was raised so that it was at a 60° angle to the direction of the furnace tube. The temperature of the dual-temperature zone was set as follows: the temperature of the side containing amorphous red phosphorus and iodine was set to rise from room temperature to 510°C at a heating rate of 5°C / min and hold for 25 h, and then cool down to room temperature at a cooling rate of 5°C / min; the temperature of the side without reagents was set to rise from room temperature to 460°C for the same heating time as the reagent-containing zone and hold for the same time, and then cool down to room temperature for the same cooling time as the reagent-containing zone. After the reaction was completed, the quartz tubes were broken, and the flaky crystalline purple phosphorus product on the tube wall was peeled off with tweezers. Flaky crystalline purple phosphorus was ground into powder, and its absorption was measured using ultraviolet-visible-near-infrared diffuse reflectance spectroscopy. The absorption curve was obtained using the Kubelka-Munk equation, and the optical band gap of the crystalline purple phosphorus was calculated to be approximately 1.89 eV using the Tauc plot method. Figure 3 As shown.

[0033] (4) The flaky crystalline phosphine product obtained in (3) was dispersed in N,N-dimethylformamide and sonicated for 8 h in a cell disruptor or ultrasonic cleaner. The temperature of the dispersion was kept constant below 30℃ during the sonication process. The dispersion after ultrasonic treatment was centrifuged at 10,000 rpm to remove the unpeeled precipitate and obtain the supernatant. The supernatant was then centrifuged at 12,000 rpm to collect the precipitate and dried in a vacuum drying oven to obtain one-dimensional Hittorf phosphine nanoribbon powder.

[0034] (5) Grind the Hittorf purple phosphorus flake crystals prepared by the iodine vapor transport method in (2) into powder using a mortar and pestle. Then, mix the powder with glucose syrup solution in a certain proportion and place it in a ball mill jar. Weigh a certain amount of grinding balls with diameters of 10 mm and 2 mm and place them in the ball mill jar. Place the ball mill jar and another ball mill jar of the same mass on a ball mill for ball milling. After ball milling, wash the slurry mixture in the ball mill jar with deionized water and remove the filtrate by filtration through a microporous membrane. Repeat the washing-filtration process three times or more to remove the glucose syrup. Finally, disperse the product filtered through the microporous membrane in deionized water and uniformly disperse it for 30 min using an ultrasonic cleaner. Then, centrifuge the dispersion at 5000 rpm, collect the supernatant, freeze the supernatant in a refrigerator to form ice cubes, and freeze-dry the ice cubes in a freeze dryer to obtain Hittorf purple phosphorus nanosheets. The optical band gap of the phosphorus nanoribbons and nanosheets, calculated using UV-Vis-NIR diffuse reflectance spectroscopy combined with the Tauc plot method, is approximately 2.4 eV. Figure 4 As shown.

[0035] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials, characterized in that, Includes the following steps: (1) Vacuum seal amorphous red phosphorus and iodine in a quartz glass tube and concentrate them on one side of the bottom; (2) Preparation of Hittorf purple phosphorus by iodine vapor transport method: The quartz tube containing amorphous red phosphorus and iodine in (1) was placed in a horizontal dual-temperature zone tube furnace. The two ends of the quartz tube were placed in the heating zone of the dual-temperature zone tube furnace, and the side without the reagent was raised so that it was at a certain angle to the direction of the tube of the tube furnace. The temperature of the dual temperature zone was set as follows: the temperature of the side containing amorphous red phosphorus and iodine was set as follows: the temperature was raised from room temperature to 460-510℃ at a certain heating rate and held for 20-25h, and then cooled to room temperature at a certain cooling rate. The temperature of the side without the reagent was set as follows: the temperature was raised from room temperature to 440-460℃ at the same heating time as the reagent zone and held for the same time, and then cooled to room temperature at the same cooling time as the reagent zone. After the reaction was completed, the quartz tube was broken and the plate-like crystalline purple phosphorus product on the tube wall was peeled off with tweezers. (3) Disperse the flaky crystalline phosphine product obtained in (2) into a solvent and place it in a cell disruptor or ultrasonic cleaner for 1-8 hours of sonication; keep the temperature of the dispersion constant below 30°C during sonication; centrifuge the dispersion after ultrasonic treatment at a speed of 5000 rpm or higher to remove the unpeeled precipitate and obtain the supernatant. Then centrifuge the supernatant at a speed of 10000 rpm or higher, collect the precipitate, and dry it in a vacuum drying oven to obtain one-dimensional Hittorf phosphine nanoribbon powder. (4) Grind the Hittorf purple phosphorus flake crystals prepared in (2) into powder using a mortar and pestle, then mix them with glucose syrup solution in a certain proportion and put them into a ball mill jar. Weigh a certain amount of grinding balls with diameters of 10 mm and 2 mm and put them into the ball mill jar. Place the ball mill jar and another ball mill jar of the same mass on a ball mill for ball milling. After ball milling, wash the slurry-like mixture in the ball mill jar with deionized water and remove the filtrate by filtration through a microporous membrane. Repeat the washing-filtration process three times or more to remove the glucose syrup. Finally, disperse the product filtered on the microporous membrane in deionized water and use an ultrasonic cleaner to disperse it evenly for 10-30 min. Then place the dispersion in a centrifuge and centrifuge at a speed of 1000 rpm or higher. Collect the supernatant and freeze it in a refrigerator to form ice cubes. Then freeze the ice cubes in a freeze dryer to obtain Hittorf purple phosphorus nanosheets. In step (4), the concentration of the glucose syrup solution is 20wt%-60wt%; the amount of glucose syrup solution and crystalline purple phosphorus used is 0.1-0.5g of crystalline purple phosphorus per 5ml of glucose syrup solution; the amount of grinding balls used is 10-20g of grinding balls per 0.1g of crystalline purple phosphorus, with 20%-30% of the grinding balls having a diameter of 10mm and 70%-80% having a diameter of 2mm; the operating parameters of the ball mill are set as follows: rotation speed 500-800rpm, forward rotation for 20-60min, reverse rotation for 20- Ball mill continuously for 12-48 hours, with intervals of 30-60 seconds, for 60 minutes. After ball milling, pour out the slurry mixture from the ball mill jar and wash it with deionized water. Remove the filtrate by filtration through a microporous membrane. Repeat the washing-filtration process 3-6 times to remove the glucose syrup. Disperse the product without glucose syrup in deionized water and use an ultrasonic cleaner to disperse it evenly for 10-30 minutes. Then, place the dispersion in a centrifuge and centrifuge at 1000-8000 rpm. Collect the supernatant and freeze-dry it to obtain Hittorf purple phosphorus nanosheets.

2. The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials as described in claim 1, characterized in that: In step (1), the purity of amorphous red phosphorus is 90%-99.9999%, the purity of elemental iodine is 99.0%-99.9%, the mass ratio of amorphous red phosphorus to elemental iodine is 10:1-30:1, and the vacuum degree of the vacuum seal is <10. -4 Pa.

3. The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials as described in claim 1, characterized in that... In step (2), both ends of the quartz tube are placed in the heating zone of a horizontal dual-temperature zone tube furnace, and the side without the reagent is raised so that it forms an angle of 5-60° with the direction of the tube furnace tube. The dual-temperature zone heating is set as follows: the side containing amorphous red phosphorus and iodine reagents is heated from room temperature to 460-510°C at a heating rate of 1-5°C / min and held for 20-25 hours, and then cooled to room temperature at a cooling rate of 1-5°C / min. The temperature of the side without the reagents is set as follows: the side is heated from room temperature to 440-460°C at the same heating time as the zone with reagents and held for the same time, and then cooled to room temperature at the same cooling time as the zone with reagents. The temperature of the two ends of the quartz tube after heating is always 20-50°C lower on the side without the reagents than on the side with the reagents.

4. The method for simultaneously preparing one-dimensional and two-dimensional Hittorf phosphorus nanomaterials as described in claim 1, characterized in that... In step (3), the solvents used are deionized water, anhydrous ethanol, isopropanol, N-methylpyrrolidone, and N,N-dimethylformamide. The amount of solvent used is 10-50 mg of crystalline purple phosphorus per milliliter of solvent. The ultrasonic time is 1-8 hours and the ultrasonic power is 120-2000 W. During the ultrasonic process, the temperature of the dispersion is kept constant at 3-30℃. The dispersion after ultrasonic treatment is centrifuged at a speed of 5000-10000 rpm.

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