CN112010274A

CN112010274A - Phosphoalkene material and preparation method and application thereof

Info

Publication number: CN112010274A
Application number: CN202010927473.1A
Authority: CN
Inventors: 喻学锋; 李睿
Original assignee: Shenzhen Institute of Advanced Technology of CAS
Current assignee: Hubei Xingfa Chemicals Group Co Ltd
Priority date: 2020-09-07
Filing date: 2020-09-07
Publication date: 2020-12-01
Anticipated expiration: 2040-09-07
Also published as: CN112010274B

Abstract

The invention discloses a phosphorus alkene material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a monomer phosphorus source and a solvent, and uniformly stirring to obtain a mixed system; reacting the mixed system under the heating condition to obtain a phospholene material; the solvent is one or the combination of at least two of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decyldiamine, diethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethanol and water; when the solvent comprises ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylamine, diethylenetriamine, ethanol and water, the heating temperature is 171-300 ℃; when the solvent comprises hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, decamethylene diamine, triethylene tetramine and tetraethylene pentamine, the heating temperature is 120-300 ℃. The antioxidant orange phosphorus phospholene with regular morphology, superior semiconductor performance and remarkably enhanced water-oxygen stability is directly prepared by using a solvothermal one-step method.

Description

Phosphoalkene material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of a preparation method of a crystalline phosphorus two-dimensional material, and relates to a phosphorus alkene material and a preparation method and application thereof.

Background

The elemental phosphorus material has a plurality of allotropes, wherein white phosphorus and red phosphorus are widely applied industrially, and black phosphorus is also widely researched and paid attention in recent years due to the unique semiconductor performance and the photoelectric and thermal characteristics of the black phosphorus. The unique two-dimensional lamellar structure of black phosphorus enables the black phosphorus to be further stripped into thin-layer black phosphorus nanosheets and even black phosphorus phospholene, so that the performance is remarkably leaped. Due to the advantages of high carrier migration rate and the like of the black phosphorus graphene, the black phosphorus graphene has great application potential in the fields of optoelectronic devices, energy sources, biomedicine and the like, the performance of the black phosphorus graphene is far superior to that of a graphene material, and the black phosphorus graphene is considered to be a very potential two-dimensional material.

However, due to the limitation of the preparation technology of the black phosphorus alkene, the mass production of the black phosphorus alkene is very difficult at present. The difficulty mainly derives from the following aspects: (1) the preparation of the black phosphorus alkene is required to rely on a high-quality black phosphorus block material at present, the preparation of the block material is required to be completed by a gas phase transmission means under the conditions of high temperature and high pressure, the instability degree is extremely high, and the industrial amplification is difficult; (2) at present, the mainstream method for converting block black phosphorus into black phosphorus grapheme by a mechanical or liquid phase stripping means is extremely time-consuming, high in cost, difficult to amplify the technology, and low in yield of the black phosphorus grapheme, so that the large-scale industrial production cannot be realized at all. Therefore, the application and development of the black phosphorus alkene are greatly limited at the present stage, and a long way is needed to be left for industrial production. In addition, a technical difficulty of the conventional black phosphorus alkene is that the stability of water and oxygen is poor, the black phosphorus alkene is easily oxidized, and even in the stripping process, the semiconductor characteristics are possibly lost due to the oxidation. In application, the serious bottleneck problem of lack of stability basically restricts the application of the black phosphorus phospholene to a laboratory stage, and has no practical significance. The above-mentioned serious defects restrict further research and development of the black phosphorus phospholene.

Therefore, the development of new phospholene materials begins to become a research hotspot in the field, but most of elemental phosphorus materials do not have a two-dimensional lamellar structure and are difficult to prepare into phospholene materials, so that only a small amount of new phospholene material preparation reports including purple phospholene, blue phospholene and the like exist at present, the preparation mode is mainly based on the traditional means, and the problems cannot be overcome. The research on the novel phospholene structure is expected to solve the major bottleneck problem of the black phospholene, and the application and the enlarged production of the phospholene material are promoted, thereby having great strategic and practical significance.

Disclosure of Invention

In order to solve the technical problems in the background art, the invention aims to provide a phospholene material, and a preparation method and application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in one aspect, the invention provides a preparation method of a phospholene material, comprising the following steps:

1) mixing a monomer phosphorus source and a solvent, and uniformly stirring to obtain a mixed system;

2) reacting the mixed system under the heating condition to obtain a phospholene material;

the solvent is one or the combination of at least two of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decyldiamine, diethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethanol and water;

when the solvent comprises ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylamine, diethylenetriamine, ethanol and water, the heating temperature is 171-300 ℃, preferably 180-280 ℃, and the conversion cannot be promoted at the excessively low temperature, so that the product is mainly the reported solvent-heated black phosphorus; when the solvent comprises hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonanediamine, decanediamine, triethylenetetramine and tetraethylenepentamine, the higher degree of freedom of curling promotes the formation of the phospholene material, and the synthesis temperature can be appropriately reduced, wherein the heating temperature is 120-300 ℃, and preferably 160-280 ℃.

Further, the phospholene material is named orange phospholene.

Further, the elemental phosphorus source in 1) is selected from one or a combination of at least two of white phosphorus, yellow phosphorus, red phosphorus, black phosphorus, purple phosphorus, blue phosphorus and scarlet phosphorus.

Further, the ratio of the elemental phosphorus source to the solvent in 1) is 0.3-20 g: 10mL, preferably 0.5-10 g: 10 mL. When the concentration of the simple substance phosphorus source is too low, white phosphorus oxide or phosphorus organic impurities can be obtained; when the concentration is too high, the mixture can be sintered into blocks in the hydrothermal kettle. Within the appropriate concentration range, increasing the feedstock concentration results in smaller diameter and more densely distributed sheets of material.

Further, the reaction time in 2) is 3 to 100 hours, preferably 6 to 100 hours. Too short a time may reduce the purity of the target product, orange phosphorus phospholene, and prolonged heating time is beneficial to improve the crystallinity of orange phosphorus phospholene, but too long a heating time may result in unnecessary increase of preparation cost.

Further, the step 2) specifically comprises: transferring the mixed system into a closed container, and reacting for a period of time under a heating condition to obtain a phospholene material;

preferably, the closed container is a hydrothermal reaction kettle;

preferably, the volume of the closed container is 1.5-3 times of the volume of the mixed system in the step 1); the self-generated pressure is increased rapidly due to too small volume of the closed container, the safety risk of preparation is improved, and waste is caused due to too large volume;

preferably, the heating comprises common oven heating, oil bath heating, heating jacket heating, rotary oven heating and other technical means capable of generating similar effects;

preferably, step 2) further comprises cooling after completion of the reaction;

preferably, the cooling includes air cooling, water bath forced cooling, and other technical means that can produce similar effects.

Further, washing and drying a product obtained by the reaction by using a cleaning solvent after the step 2);

preferably, the cleaning solvent is selected from one or a combination of at least two of ethanol, acetone, Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and water;

preferably, the drying comprises ordinary oven drying, vacuum oven drying and other technical means capable of generating similar effects;

preferably, the drying temperature is 50-100 ℃;

preferably, the drying time is 6 hours to 2 days, preferably overnight (about 10 to 14 hours);

preferably, whether the low-temperature firing treatment is carried out in an inert gas atmosphere or not can be selected according to requirements so as to completely remove the adsorbed trace amine solvent, and the low temperature is below 400 ℃.

Further, the method comprises the step of carrying out dispersion treatment on the phosphorus alkene material to obtain a monodisperse phosphorus alkene material with better dispersibility;

preferably, the dispersion treatment adopts a method comprising common dispersion technologies such as ball milling, water bath ultrasound, probe ultrasound and the like.

In another aspect, the invention provides a phospholene material prepared by any one of the above-mentioned methods for preparing a phospholene material.

In another aspect, the invention provides an application of the above-mentioned phosphorus alkene material in the fields of photo/electro-catalytic reaction, battery electrode material, semiconductor photoelectric element, flame retardant material, tumor tracing treatment, and the like.

The invention has the beneficial effects that: the invention uses the solvothermal one-step method to directly prepare the phospholene material in batches, the method has simple process, low cost, high yield, large amplification production space and mature technology, is convenient for realizing industrialized mass production, and the product spontaneously grows into a thin layer structure with the sheet diameter of about 200nm, and the thickness of most of the thin layer is below 10nm, so that a large amount of monodisperse orange phospholene products can be obtained only by simple redispersion without the traditional stripping means with high energy consumption and no amplification.

The high-performance antioxidant orange phosphorus phospholene material with regular morphology, superior semiconductor performance and remarkably enhanced water-oxygen stability is prepared by the method, the typical p-type semiconductor characteristic of the material is expected to be widely applied in the fields of catalytic reaction, semiconductor elements and the like, the two-dimensional lamellar morphology and large theoretical capacity are expected to be applied in the fields of battery electrodes, flame retardance and the like, and the low biological toxicity also enables the application in organisms to be possible. Compared with the existing phosphorus alkene material, especially black phosphorus alkene, the storage life of the orange phosphorus alkene is prolonged to several years, the cognition range of the existing phosphorus alkene material in the appearing stage industry is greatly exceeded, the traditional cognition of the phosphorus material with poor water oxygen stability is overturned, and the possibility of practical application of the phosphorus alkene material is also ensured. The orange phosphorus phospholene and the solution heat preparation method thereof simultaneously solve the three bottleneck problems of the black phosphorus phospholene in the background technology, have profound and remote meanings in multiple aspects, and simultaneously greatly improve the yield and the quality to lay a solid foundation for developing the industrial practical application of the two-dimensional phosphorus material.

Drawings

FIG. 1 is a photograph of an orange phospholene in example 1 of the present invention.

FIG. 2 is an XRD pattern of orange phospholene in example 1 of the present invention.

FIG. 3 is an SEM picture of orange phospholene in example 1 of the present invention.

FIG. 4 is a photograph of an ethanol dispersion after redispersion of orange phospholene in example 1 of the present invention.

FIG. 5 is a TEM image of orange phospholene after redispersion in example 1 of the invention.

FIG. 6 is an AFM picture of redispersed orange phospholimonene of example 1 of the present invention and a corresponding analysis of lamella thickness.

FIG. 7 is a Raman spectrum of orange phospholene in example 1 of the present invention.

FIG. 8 is an XRD pattern of orange phospholene in example 2 of the present invention.

FIG. 9 is an XRD pattern of orange phospholene in example 3 of the present invention.

FIG. 10 is a schematic diagram of red phosphorus as a raw material and a phosphorus alkene material prepared at a corresponding time in example 5 of the present invention.

FIG. 11 is an XRD pattern of orange phospholene of example 5 of the present invention.

FIG. 12 is an XRD pattern of orange phospholene in the presence of propanediamine as solvent in example 6 of the present invention.

FIG. 13 is an XRD pattern of orange phospholene of example 7 of the present invention.

Fig. 14 is a semiconductor performance test chart of the orange phosphorus phospholene material obtained in example 1 of the present invention, where (a) is an ultraviolet-visible light-near infrared diffuse reflection chart, fig. (b) is an ultraviolet photoelectron energy spectrum, fig. (c) is an X-ray photoelectron energy spectrum, and fig. (d) is a band gap structure diagram.

Fig. 15 is XPS detection of orange phospholene obtained in inventive example 1 and black phospholene obtained in comparative example 1 using a conventional method.

FIG. 16 is an AFM scan of orange phospholene obtained in inventive example 1 and black phospholene material obtained in comparative example 1 using conventional methods.

FIG. 17 is an XPS survey of fresh orange phospholene and orange phospholene left in air for 13 months in example 1 of the invention.

FIG. 18 is a TEM examination of fresh orange phospholene and orange phospholene left in air for 13 months in example 1 of the present invention.

Fig. 19 is a graph showing the performance of the black phospholene obtained by the conventional method in comparative example 1 and the orange phospholene obtained in example 1 of the present invention after redispersion for electrocatalytic and photoelectrocatalytic hydrogen evolution reactions, in which (a) is a linear sweep voltammogram and tafel slope in the electrocatalytic hydrogen evolution reaction, (b) is a linear sweep voltammogram and tafel slope in the photoelectrocatalytic hydrogen evolution reaction, and (c) is a time current I-t curve of the electrocatalytic and photoelectrocatalytic hydrogen evolution reactions.

Detailed Description

For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings, and the scope of the invention is not limited to the following examples.

Comparative example 1

Black phospholene material, also around 200nm, was prepared using conventional CVT-stripping means for comparison with orange phospholene with similar sheet diameter and thickness. The preparation process of the black phosphorus phospholene comprises the following steps: 3g of red phosphorus, 0.12g of Sn and 0.06g of iodine are used, and the inner diameter is measured at the sintering temperature of 510 DEG C

The black phosphorus block material is prepared in a quartz tube with the length of 10cm, and the preparation time is 18 hours. And then dispersing the block black phosphorus material in NMP by water bath ultrasound for 10 hours, carrying out ultrasound for 10 hours by using a probe to peel the block black phosphorus material into a micro-nano sheet, and finally carrying out centrifugal separation at 7000rpm to obtain an upper layer product, namely the ideal black phosphorus alkene material with the wavelength of about 200 nm.

Example 1

(1) Weighing 1g of 6N high-purity red phosphorus raw material, adding the raw material into 10mL of tetraethylenepentamine solvent, and magnetically stirring for 2 hours at room temperature to uniformly disperse the red phosphorus raw material in the solvent;

(2) transferring the mixed system into a 25ml hydrothermal reaction kettle, screwing down a reaction kettle cover, and heating in a common oven at 220 ℃ for 18 hours;

(3) after the reaction kettle is cooled to room temperature in the air, the obtained powder product is washed and centrifuged for many times by using ethanol, and residual solvent is washed away.

(4) Drying the washed reddish-brown solid in a common oven at 80 ℃ overnight to obtain powdery orange phosphorus phospholene material with the yield of more than 80%, wherein the photo of the substance is shown in figure 1. The XRD pattern of the orange phospholene is shown in figure 2, and the structure of the orange phospholene is the same as that of the reported bulk elemental phosphorus (PDF #44-0906) standard sample from figure 2, which shows that the orange phospholene and the orange phospholene have the same crystal structure. As shown in FIG. 3, the SEM image of orange phospholene shows that the diameter of the spontaneously formed phospholene sheet is about 200nm and the thickness of the sheet is 10nm or less, as shown in FIG. 3.

In order to better embody the performance, the low-energy-consumption probe is adopted to perform the dispersion treatment on the orange phosphorus phospholene material in the embodiment, the ultrasonic power is 500W, and the time is 10 hours. As shown in FIG. 4, the orange phospholene ethanol dispersion after dispersion treatment has a large yield, and thus a large amount of orange ethanol dispersion can be obtained (the orange color is not shown after the black-and-white image is obtained). The TEM of the dispersed orange phospholene is shown in fig. 5, and it can be seen from fig. 5 that the lamella of the dispersed orange phospholene is uniform and independent, almost no agglomeration exists, the lamella size is slightly reduced, but basically about 200 nm. AFM pictures of the orange phospholene after dispersion treatment are shown in FIG. 6, and the thickness of the phospholene lamella therein is analyzed, and the thickness is found to be less than 10 nm.

The raman spectrum of the orange phospholene is shown in fig. 7, and the raman vibration mode of the orange phospholene is compared with that of the raw material red phosphorus and the traditional black phospholene (comparative example 1), and it can be known from fig. 7 that the orange phospholene is closer to the red phosphorus raw material and has a certain difference with the vibration mode of the black phospholene. Whether the dispersion treatment is carried out or not has no influence on the Raman vibration mode.

Example 2

The raw materials in the step (1) are replaced by 5N high-purity red phosphorus, 98.5 percent common red phosphorus (AR), industrial white phosphorus and black phosphorus prepared by solvothermal method, and the rest conditions are the same as those in the example 1. XRD detection is carried out on the prepared phospholene material, as shown in figure 8, as can be seen from figure 8, the crystal structure is not changed, and the obtained phospholene material is still orange.

Example 3

The raw material concentration in step (1) was adjusted to 0.5g, 5g, 8g, 10g of the raw material containing red phosphorus per 10mL of the solvent, and the other conditions were the same as in example 1. XRD detection is carried out on the prepared phospholene material, as shown in figure 9, as can be seen from figure 9, the crystal structure is not changed, and the obtained phospholene material is still orange.

Example 4

The heating temperature in the step (2) was adjusted to 140, 160,180, 200, 240, 260, and 280 ℃ under the same conditions as in example 1. XRD detection is carried out on the prepared phospholene material, and the proportion of the orange phospholene in the product is more than 50 percent when the heating temperature is more than 160 ℃ according to the XRD detection.

Example 5

The heating time in step (2) was adjusted to 3, 6, 9, and 96 hours, and the other conditions were the same as in example 1. A physical diagram of the red phosphorus raw material and the phosphorus alkene material prepared at the corresponding time is shown in FIG. 10 (the macro morphology of the 96-hour sample is not different from that of the 9-hour sample, so that the macro morphology is not shown in FIG. 10). XRD detection is carried out on the prepared phospholene material, as shown in figure 11, as can be seen from figure 11, the crystal structure is not changed, and the obtained phospholene material is still orange. And XRD detection shows that the heating time is over 6 hours, and the obtained product is basically orange phosphorus phospholene. Since the orange phospholene is converted from solvothermal black phosphorus, heating for less than 6 hours leaves solvothermal black phosphorus impurities in the product, resulting in a product that appears black (as shown in fig. 10), with peaks of impurities in the solvothermal black phosphorus in the XRD (as shown in fig. 11).

Example 6

The solvent used was replaced with a short-chain solvent such as ethylenediamine, propylenediamine, diethylenetriamine, and the heating temperature was adjusted to 140, 160,180, 200, 220, and 240 ℃, and the other conditions were the same as in example 1. XRD detection shows that the three solvents have similar effects, and the XRD pattern of the propanediamine is taken as the demonstration, as shown in figure 12, as can be seen from figure 12, the phospholene material cannot be prepared at 140 ℃ and 160 ℃ when the short-chain solvent is used, and when the heating temperature is more than 200 ℃, the obtained product is mainly orange phospholene.

Example 7

The solvent used was replaced with hexamethylenediamine, a long-chain solvent, and the heating temperature was adjusted to 160 ℃ under the same conditions as in example 1. XRD detection is carried out on the prepared phospholene material, and as shown in figure 13, the obtained product contains impurities, but the orange phospholene material is still taken as the main material.

Example 8

The common oven heating in the step (2) is changed into oil bath heating or heating sleeve heating, and products are not obviously different. If the magnet is added into the hydrothermal kettle for stirring when the oil bath/heating jacket is used for heating, or the hydrothermal kettle is heated by using a rotary oven, the obtained material has smaller particle size and more broken shape (the thickness is not changed greatly, and the sheet diameter can be as small as about 100nm or even smaller) due to the additional crushing effect, but the crystal type is not obviously influenced.

Example 9

The cooling mode of the reaction kettle in the step (3) is changed into a water bath forced cooling mode, and the obtained product is not influenced.

The washing solvent is changed into acetone, DMF, NMP and water, and the product obtained is not affected.

According to the requirement, heating at about 300 ℃ in a nitrogen atmosphere can be selected to remove trace residual solvent, and XRD detection shows that the structure of the product orange phosphorus phospholene after heating treatment is still complete (the graph line is the same as that in figure 2).

Example 10

The drying temperature of the product in the step (4) is adjusted to be 50, 60, 80 and 100 ℃, the drying time is adjusted to be 6 hours, 12 hours, 18 hours, 24 hours and 72 hours, and the crystallinity of the obtained product is not influenced (the XRD graph is the same as that in figure 2).

The product is not obviously affected by drying in a common oven or a vacuum oven.

Simple and low-energy-consumption technology can be selected to further improve the dispersion degree of the orange phosphorus phospholene in different solvent systems, reduce the agglomeration of large particles and prepare dispersion liquid. The technical means include but are not limited to ball milling, water bath ultrasound, probe ultrasound and other common dispersion techniques.

Example 11

Ultraviolet-visible light-near infrared diffuse reflection, ultraviolet electron spectroscopy and X-ray photoelectron spectroscopy analysis are carried out on the orange phospholene material obtained in example 1, and the results are respectively shown in FIGS. 14a-c, from which it can be seen that the valence band of orange phospholene is 1.06eV, and belongs to a p-type semiconductor, and the schematic diagram of the band gap structure thereof is shown in FIG. 14 d.

Example 12

The orange phospholene obtained in example 1 was compared to the black phospholene material obtained in comparative example 1 using conventional methods for water oxygen stability under different conditions (overall stability is higher when the total amount of material is higher). After storing for 1-5 days at 35 deg.C and 100% humidity, XPS test is performed, as shown in FIG. 15, it can be seen from FIG. 15 that most of the black phosphorus phospholene is oxidized on day 2, and all the black phosphorus phospholene is oxidized on day 5, while more than half of the material of the orange phosphorus phospholene remains intact and unoxidized after day 5.

The difference in stability of the individual phospholenes is more readily apparent than when the material is present in large amounts. Referring to fig. 16, when the orange phospholene obtained in example 1 and the black phospholene material obtained in comparative example 1 by using the conventional method are scanned by AFM, as shown in fig. 16, it can be seen from fig. 16 that the black phospholene has oxidation bubbles (marked by arrows) during the scanning process (about 1-2 hours), while the orange phospholene has a smooth surface and no oxidation sign after being stored in air for one day at room temperature.

Example 13

The orange phospholene obtained in example 1 was prepared as a suspension in ethanol and stored in air for more than one year (13 months), and XPS detection was performed on fresh orange phospholene and orange phospholene stored for more than one year, respectively, as shown in fig. 17, XPS analysis showed that orange phospholene stored for more than one year was only slightly oxidized compared to fresh orange phospholene. TEM detection is carried out on fresh orange phospholene and orange phospholene stored for more than one year respectively, and as shown in FIG. 18, TEM analysis shows that the crystal lattice structure of the orange phospholene crystal stored for more than one year is still complete, and the crystal lattice structure is not obviously changed compared with that of the fresh orange phospholene. Even if the black phosphorus alkene is stored in a glove box which is isolated from water and oxygen as much as possible, the black phosphorus alkene can be completely oxidized and disappear in about 4 months.

Example 14

Based on the excellent stability and semiconductor characteristics of the orange phospholene, the performance of the orange phospholene is compared with the traditional black phospholene in the comparative example 1 in the electrocatalysis and photoelectrocatalysis hydrogen evolution reactions, and as shown in fig. 19, the activity and stability of the orange phospholene are obviously superior to those of the black phospholene. As can be seen from fig. 19a, b, the Linear Sweep Voltammogram (LSV) shows that the overpotential of orange phospholene is significantly lower and the tafel slope is smaller when the same hydrogen evolution current is generated; as can be seen from FIG. 19c, the I-t plot of the chronoamperometric current indicates that the percent of residual current of orange phospholene is 3-4 times that of black phospholene, while the rate of decay is less than one tenth of the latter. The results prove that the orange phospholene is a better electro-catalysis and photo-electro-catalysis hydrogen evolution catalyst than the black phospholene, and has bright application prospect in other application fields, such as semiconductor elements, battery electrodes, biological medicines, flame retardance and the like.

In conclusion, the high-performance antioxidant orange phosphorus phospholene material with regular morphology, superior semiconductor performance and obviously enhanced water-oxygen stability is prepared by the method, and the orange phosphorus phospholene is a better electro-catalysis and photo-electro-catalysis hydrogen evolution catalyst than black phosphorus phospholene, and has bright application prospects in other application fields, such as semiconductor elements, battery electrodes, biological medicines, flame retardance and the like.

The above description is only a specific embodiment of the present invention, and not all embodiments, and any equivalent modifications of the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.

Claims

1. The preparation method of the phosphorus alkene material is characterized by comprising the following steps:

when the solvent comprises ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylamine, diethylenetriamine, ethanol and water, the heating temperature is 171-300 ℃, preferably 180-280 ℃; when the solvent comprises hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, decamethylene diamine, triethylene tetramine and tetraethylene pentamine, the heating temperature is 120-300 ℃, and is preferably 160-280 ℃.

2. The method of making a phosphene material of claim 1, wherein the phosphene material is named orange phosphene.

3. The method for preparing the phospholene material according to claim 1, characterized in that the elemental phosphorus source in 1) is selected from one or a combination of at least two of white phosphorus, yellow phosphorus, red phosphorus, black phosphorus, purple phosphorus, blue phosphorus and scarlet phosphorus.

4. The preparation method of the phosphorus alkene material of claim 1, wherein the ratio of the elemental phosphorus source to the solvent in 1) is 0.3-20 g: 10mL, preferably 0.5-10 g: 10 mL.

5. The method of claim 1, wherein the reaction time in 2) is 3 to 100 hours, preferably 6 to 100 hours.

6. The method for preparing the phospholene material according to claim 1, characterized in that step 2) specifically comprises: transferring the mixed system into a closed container, and reacting for a period of time under a heating condition to obtain a phospholene material;

preferably, the closed container is a hydrothermal reaction kettle;

preferably, the volume of the closed container is 1.5-3 times of the volume of the mixed system in the step 1);

preferably, the heating comprises common oven heating, oil bath heating, heating sleeve heating and rotary oven heating;

preferably, step 2) further comprises cooling after completion of the reaction;

preferably, the cooling comprises air cooling, water bath forced cooling.

7. The method for preparing a phospholene material according to any of the claims 1-6, characterized in that step 2) is followed by washing and drying the product of the reaction with a washing solvent;

preferably, the cleaning solvent is selected from one or a combination of at least two of ethanol, acetone, DMF, NMP, water;

preferably, the drying comprises ordinary oven drying and vacuum oven drying;

preferably, the drying temperature is 50-100 ℃;

preferably, the drying time is from 6 hours to 2 days, preferably overnight;

8. The method of producing a phosphene material of any one of claims 1 to 7 further comprising subjecting the phosphene material to a dispersion treatment;

preferably, the dispersion treatment adopts methods including ball milling, water bath ultrasound and probe ultrasound.

9. The phospholene material prepared by the method of preparation of a phospholene material according to any of the claims from 1 to 8.

10. The use of the phospholene material of claim 9 in the fields of photo/electrocatalytic reactions, battery electrode materials, semiconductor photovoltaic elements, flame retardant materials and tumor tracing treatments.