CN113912030B - Modified black phosphorus alkene, and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of preparation and application of novel two-dimensional material black phosphorene, and discloses a modified black phosphorene and a preparation method and application thereof. The preparation method firstly uses black phosphorus crystals to make black phosphorene, then uses black phosphorene and polyazide compound to make black phosphorene mixed solution, and finally heats the black phosphorene mixed solution to obtain modified black phosphorene. In the present invention, the azide group of the polyazide compound is reacted with the surface of the black phosphorene to generate a P=N group, which can increase the stability of the black phosphorene in the air, and the prepared modified black phosphorene also has black phosphorene. The good characteristics of phosphorus nanosheets themselves: good carrier mobility, tunable band gap and high anisotropy, etc. Therefore, the modified black phosphorene prepared by the present invention can be widely used in catalyst materials, electrochemical materials or aerospace materials.

Description

A kind of modified black phosphorene and its preparation method and application

technical field

The invention relates to the technical field of preparation and application of novel two-dimensional material black phosphorene, in particular to a modified black phosphorene and a preparation method and application thereof.

Background technique

In 2014, a new two-dimensional material single-layer black phosphorus-black phosphorene (PN) was prepared by tape technology. Compared with graphene, black phosphorene has a maximum theoretical surface area of 2400m ² g ^-1 , which has a higher surface area. The electrical conductivity (carrier mobility reaches 160000cm ² /(V·s)) and thermal conductivity (the thermal conductivity is 8500W/(m·K)), at the same time, black phosphorene can react with O ₂ to release a lot of heat, phase Energy inert than graphene, black phosphorene can be used as an energetic component. However, the application process of black phosphorene still faces a very big problem, that is, it is easily degraded in the air. The reason is: black phosphorene has a strong dipole moment out of the plane, which makes the surface of black phosphorene easy to adsorb water. and oxygen to generate phosphorus oxides to degrade. In order to expand the application field of black phosphorene, the stability of black phosphorene has been studied, but the research results are not ideal. The reason is: while stabilizing black phosphorene in air, a certain amount of other element atoms or radicals will be introduced. group, thereby changing the physicochemical properties of black phosphorene, which in turn affects its practical application. Especially when black phosphorene is introduced into energetic composites, the energy level of the system will decrease due to the introduction of new elements or groups.

In addition, some researchers found that when black phosphorene nanosheets were used as two-dimensional nanofillers to strengthen polyvinyl alcohol (PVA) matrix, they found that when the addition amount was 3.11wt%, the maximum tensile strength was 316.9MPa, which is the best of pure PVA. 1.9 times, and with the further increase of the addition amount, the mechanical properties begin to decline. The reason for this result is the agglomeration of black phosphorene nanosheets.

Therefore, how to solve the easy oxidation of black phosphorene in the air and the easy agglomeration of black phosphorene when it is used as a two-dimensional filler to reinforce the matrix has become an urgent problem for those skilled in the art to solve.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a modified black phosphorene and a preparation method and application thereof, which effectively solve the phenomenon that black phosphorene is easily oxidized in the air and the phenomenon that black phosphorene is prone to agglomeration when it is used as a two-dimensional filler to reinforce a matrix, etc. technical problem.

In order to achieve the above object, the present invention adopts the following technical solutions:

The invention provides a preparation method of modified black phosphorene, comprising the following steps:

S1, prepare the black phosphorus crystal into a BP-water solution, and then prepare the BP-water solution into black phosphorene;

S2, dispersing the black phosphorene obtained in step S1 in a reaction solvent to obtain a black phosphorene dispersion, and then adding a polyazide compound to the black phosphorene dispersion to obtain a black phosphorene mixed solution;

S3, heat-treating the black phosphorene mixed solution obtained in step S2 to generate modified black phosphorene;

The above steps are all carried out under protective gas.

In the step S1, the concentration of the BP-water solution is 1-10 mg/mL.

In the step S2, the solubility ratio of black phosphorene to the reaction solvent is 1-5 mg/mL, and the mass ratio of black phosphorene to the polyazide compound is 1:50-70;

The reaction solvent is one or more of N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and polyethylene glycol.

In the step S2, the polyazido compound is polyazide glycidyl ether, poly-3-azidomethyl-3, methyloxetane, poly-3,3-diazidomethyloxetane One or more of cyclobutane and 3,3-bisazidomethyl butylene oxide-tetrahydrofuran copolyether.

In the step S2, the polyazide compound is added and then stirred to obtain a black phosphorene mixed solution; the stirring speed is 100-1500 rpm, and the stirring time is 1-5 h.

The protective gas is one of nitrogen, argon, helium, neon and carbon dioxide.

In the step S3, during the heat treatment, the temperature is raised to 100-200°C at a rate of 2-10°C/min, and then kept for 12-60h.

The heat-treated mixture is then cooled, centrifuged, washed and dried to obtain modified black phosphorene;

The cooling temperature is room temperature;

The time of the centrifugation is 10～30min, and the rotating speed of the centrifugation is 3000～10000rpm;

During the washing, first use the reaction solvent to wash, and then wash with water or ethanol;

The drying method is one of critical point drying, supercritical drying, vacuum drying and freeze drying in which the medium is carbon dioxide.

The present invention provides modified black phosphorene prepared by the above method.

The present invention also provides an application of the above-mentioned modified black phosphorene in catalyst materials, electrochemical materials or aviation materials.

The principle of the technical solution of the present invention is as follows: the P element on the PN surface and the azide group of the azide polymer form a P=N double bond, occupy the lone pair of electrons on the surface of the P element, and realize the five-coordinate bond of the phosphorus atom, thereby The lone pair electrons are prevented from reacting with water and oxygen in the air, resulting in complete passivation of PNs.

As can be seen from the above-mentioned technical solutions, compared with the prior art, the beneficial effects of the present invention are as follows:

1. The black phosphorene prepared by the method of the present invention has the characteristics of being stable in air and not being oxidatively degraded.

2. The method of the present invention uses a polyazide compound as a black phosphorene stabilizing modifier, and when the black phosphorene is introduced into the energy-containing composite material, the energy level of the system will not decrease.

3. The method of the present invention uses a polyazide compound as a black phosphorene stabilizing modifier, and introduces a system with active hydroxyl groups that can participate in polyurethane and other systems that can react with hydroxyl groups, improve interfacial force, promote compatibility, and reduce agglomeration phenomenon and improve the mechanical properties of the system.

4. The preparation process of the present invention is simple and controllable.

5. Since the processing and drying equipment used in the present invention is simple and common, and does not need to add expensive equipment, it belongs to the low-cost experimental green preparation process.

6. The present invention utilizes the azide group of the polyazide compound to react with the surface of the black phosphorene to generate a P=N group, which can increase the stability of the black phosphorene in the air, and the prepared modified black phosphorene also It has the good characteristics of black phosphorus nanosheet itself: good carrier mobility, tunable band gap and high anisotropy, etc. Therefore, the modified black phosphorus prepared by the present invention can be widely used in catalyst materials, Electrochemical materials or aerospace materials and other fields.

Description of drawings

In Fig. 1, a and b are the TEM and HR-TEM images of the PNs obtained in Example 1, respectively, c and d are the TEM and HR-TEM images of the GAP-PN obtained in Example 1, and e are Mapping images for STEM images and STEM-edx elements of GAP-PN;

Fig. 2 is the reaction process diagram of GAP-functionalized PNs;

In Figure 3, (a) and (b) are the 3DAFM images and AFM images of the PNs obtained in Example 1, respectively, and (c) and (d) are the 3DAFM images of GAP-PNs obtained in Example 1, respectively and AFM images, (e) and (f) are the height maps of PNs and GAP-PN obtained in Example 1, respectively;

In Figure 4, (a) is the Raman spectrum of the PNs and GAP-PN obtained in Example 1, (b) is the ³¹ P-NMR spectrum of the original PNs and GAP-PN (* is the spin sideband) Peak), (c) and (d) are the XPS spectra of the original PNs and GAP, respectively, (e) and (f) are the XPS spectra of the GAP-PN obtained in Example 1;

Fig. 5 is the reaction mechanism diagram of the formation of P=N double bond between P element and GAP azide group on the surface of PN;

In Figure 6, (a) and (c) are the XPS spectra of PNs and GAP-PN-48h obtained in Example 1, respectively, and (b) and (d) are the samples obtained in Example 1 in air, respectively. XPS spectra of PNs and GAP-PN-48h after being placed in DI water for 30 days; (e-g) Figures show that PNs, GAP-PN-12h and GAP-PN-48h obtained in Example 1 were dispersed in DI water and placed in air for 1 , 7, 14, 21, 28, 35, 49 and 63 days of UV/Vis absorption spectra; (h) the picture shows the degradation ratio of PNs, GAP-PN-12h and GAP-PN-48h (1-A/A0 );

In Fig. 7, (a) is the DSC chart (10°C/min) of PNs, GAP-PN and GAP obtained in Example 1, and (b) is released during the decomposition of PNs and GAP-PN obtained in Example 1 of heat.

Detailed ways

The invention provides a preparation method of modified black phosphorene, comprising the following steps:

S1, prepare the black phosphorus crystal into a BP-water solution, and then prepare the BP-water solution into black phosphorene;

S2, dispersing the black phosphorene obtained in step S1 in a reaction solvent to obtain a black phosphorene dispersion, and then adding a polyazide compound to the black phosphorene dispersion to obtain a black phosphorene mixed solution;

S3, heat-treating the black phosphorene mixed solution obtained in step S2 to generate modified black phosphorene;

The above steps are all carried out under protective gas.

In step S1 of the present invention, the concentration of the BP-water solution is 1-10 mg/ml, preferably 1-7 mg/ml.

Preferably, the BP-water solution is added to a beaker, placed in an ice bath, and placed in a cell disrupter. Under a protective gas atmosphere, the bottom of the sample is 1.5-3 cm away from the ultrasonic probe, and the ultrasonic power is 45-95%. Work in 4s mode for 2 to 30h, and then centrifuge and freeze-dry to obtain black phosphorene;

Further preferably, the ultrasonic work is performed for 8-20 hours, and the ultrasonic power is 45-80%.

Preferably, during centrifugation, the rotating speed is 5000～10000rpm, and the centrifugation time is 5～20min; the freezing temperature during freeze drying is -50～-10°C, and the time is 8～12h;

Further preferably, during centrifugation, the rotating speed is 7000-10000 rpm, and the centrifugation time is 10-15 min; the freezing temperature during freeze-drying is -50--30°C, and the time is 10-12 h.

In the step S2 of the present invention, the black phosphorene obtained in the step S1 is ultrasonically dispersed in the reaction solvent, the ultrasonic power is 45-95%, and the time is 30-120 minutes; then polyazide is added to the dispersion of the black phosphorene. The compound is treated with mechanical stirring at 100-1500 rpm for 1-5 hours to obtain a uniform black phosphorene mixed solution.

Preferably, the ultrasonic power is 60-95%, and the ultrasonic time is 30-60 minutes.

Preferably, the solubility ratio of black phosphorene to the reaction solvent is 3-5 mg/mL, and the mass ratio of black phosphorene to the polyazide compound is 1:50-60;

Further preferably, the solubility ratio of black phosphorene to the reaction solvent is 4 mg/mL, and the mass ratio of black phosphorene to the polyazide compound is 1:60;

Preferably, the reaction solvent is N,N-dimethylformamide.

Preferably, the polyazide compound is polyazide glycidyl ether.

Preferably, the polyazide compound is added to the dispersion liquid of black phosphorene, and the mixture is mechanically stirred at 250-1000 rpm for 1-3 hours.

In the step S3 of the present invention, the black phosphorene mixture obtained in the step S2 is placed in a Shrek tube, firstly frozen with liquid nitrogen, then evacuated to a vacuum state by a vacuum pump, and then a protective gas is introduced, repeating 3 times, and then heated to 100-200°C at a rate of 2-10°C/min, kept for 12-60 hours, and after cooling, the mixture was centrifuged at 3,000-10,000 rpm for 10-30 minutes, then washed with the reaction solvent first, and then washed with deionized water. , each washed 3 to 10 times, and then dried for 3 to 10 hours to obtain modified black phosphorene.

Preferably, during heat treatment, the temperature is raised to 150-200°C at a rate of 5-7°C/min.

Preferably, during centrifugation, the centrifugation time is 10-20 min, and the centrifuging speed is 5000-7000 rpm.

Preferably, the reaction solvent and deionized water are each washed 3-7 times, and then dried for 3-7 hours.

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 1 mg/ml of BP-water solution. The beaker was placed in an ice bath, placed in a cell disruptor, and in an argon atmosphere, the bottom of the sample was 2 cm away from the ultrasonic probe, the ultrasonic power was 45%, and the ultrasonic wave was turned on for 2 s and turned off for 4 s for 8 h, and then centrifuged at 7000 rpm. 10min, freeze-drying at -50℃ for 10h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (50 mg) obtained in step S1 in N,N-dimethylformamide (DMF, 10 mL), the ultrasonic power is 95%, and the time is 30 minutes; Polyglycidyl azide (GAP, 3 g) was added, and the mixture was mechanically stirred at 250 rpm for 1 hour to obtain a uniform black phosphorene mixture. The whole process was carried out under argon.

S3. Put the black phosphorene mixture obtained in step S2 into a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then pass argon gas, repeat 3 times, and then heat it at 5°C The temperature was raised to 150°C at a rate of /min, kept for 12h, and after cooling, the mixture was centrifuged at 7000rpm for 10min, then washed with N,N-dimethylformamide and deionized water 3 times each, and then dried for 3 hours. Modified black phosphorene.

到

)，说明GAP聚合物插入PNs]的层间，使层间距离变大；TEM-EDX测试表明，磷(P)、氮(N)、碳(C)、氧(O)元素均匀分散在整个纳米片中。It can be seen from Figure 1 of the present invention that PNs and GAP-PN have a typical multi-layer structure, and black substances can be observed on the surface of GAP-PN, which are GAP polymers grafted on the surface of PNs; distance expanded by 36% (from

arrive

), indicating that the GAP polymer is inserted into the interlayer of PNs], making the interlayer distance larger; TEM-EDX test shows that phosphorus (P), nitrogen (N), carbon (C), and oxygen (O) elements are uniformly dispersed throughout the in nanosheets.

It can be seen from FIG. 3 of the present invention that the thickness pairs of PNs and GAP-PN are relatively average, the height of PNs at the scribed line is 4.37 nm, and the height of GAP-PN is 10.4 nm.

It can be seen from FIG. 4 of the present invention that a novel covalently functionalized black phosphorus nanosheet (GAP-PN) containing P=N double bonds was synthesized.

It can be seen from Figure 6 of the present invention that the GAP-PN prepared by the present invention has good stability. After being placed in the air for 60 days, the degradation rates of PNs and GAP-PN-48h are 54.9% and 8.8%, respectively.

It can be seen from Figure 7 of the present invention that compared with PNs, the exothermic peak temperature (T _P ) of GAP-PN is reduced by 44.6 °C, and the exothermic heat during the decomposition process is as high as 3154.9 J/g, which is 6.09 times that of PNs.

Example 2

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 1 mg/ml of BP-water solution. Put the beaker in an ice bath, put it into the cell disruptor, under a nitrogen atmosphere, the bottom of the sample is 2 cm away from the ultrasonic probe, the ultrasonic power is 45%, and the ultrasonic is turned on for 2 s and turned off for 4 s for 8 h, and then centrifuged at 7000 rpm for 10 min , freeze-drying at -50℃ for 10h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (50 mg) obtained in step S1 in N,N-dimethylformamide (DMF, 10 mL), the ultrasonic power is 95%, and the time is 30 minutes; Polyglycidyl azide (GAP, 3 g) was added, and the mixture was treated with mechanical stirring at 250 rpm for 1 hour to obtain a uniform black phosphorene mixture. The whole process was carried out under nitrogen.

S3. Place the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, and then use a vacuum pump to evacuate it to a vacuum state, and then introduce nitrogen gas, repeat 3 times, and then at 5°C/ The temperature was raised to 150°C at a min rate and kept for 24h. After cooling, the mixture was centrifuged at 7000rpm for 10min, washed with N,N-dimethylformamide and deionized water for 3 times each, and dried for 3 hours. Sexual black phosphorene.

Example 3

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 1 mg/ml of BP-water solution. Put the beaker in an ice bath, put it into the cell disrupter, under a helium atmosphere, the bottom of the sample is 2 cm away from the ultrasonic probe, the ultrasonic power is 45%, and the ultrasonic is turned on for 2 s and turned off for 4 s for 8 h, and then centrifuged at 7000 rpm. 10min, freeze-drying at -50℃ for 10h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (50 mg) obtained in step S1 in N,N-dimethylformamide (DMF, 10 mL), the ultrasonic power is 95%, and the time is 30 minutes; Polyazide glycidyl ether (GAP, 3 g) was added, and the mixture was mechanically stirred at 250 rpm for 1 hour to obtain a uniform black phosphorene mixture. The whole process was carried out under helium gas.

S3. Put the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then pass helium gas, repeat 3 times, and then heat it at 5°C The temperature was raised to 150°C at a rate of /min, kept for 36h, and after cooling, the mixture was centrifuged at 7000rpm for 10min, then washed with N,N-dimethylformamide and deionized water 3 times each, and then dried for 3 hours. Modified black phosphorene.

Example 4

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 1 mg/ml of BP-water solution. Put the beaker in an ice bath, put it into the cell disrupter, under a helium atmosphere, the bottom of the sample is 2 cm away from the ultrasonic probe, the ultrasonic power is 45%, and the ultrasonic is turned on for 2 s and turned off for 4 s for 8 h, and then centrifuged at 7000 rpm. 10min, freeze-drying at -50℃ for 10h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (50 mg) obtained in step S1 in N,N-dimethylformamide (DMF, 10 mL), the ultrasonic power is 95%, and the time is 30 minutes; Polyazide glycidyl ether (GAP, 3 g) was added, and the mixture was mechanically stirred at 250 rpm for 1 hour to obtain a uniform black phosphorene mixture. The whole process was carried out under helium gas.

S3. Put the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then pass helium gas, repeat 3 times, and then heat it at 5°C The temperature was raised to 150°C at a rate of /min, kept for 48h, and after cooling, the mixture was centrifuged at 7000rpm for 10min, then washed with N,N-dimethylformamide and deionized water 3 times each, and then dried for 3 hours. Modified black phosphorene.

Example 5

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 3 mg/ml of BP-water solution. Put the beaker in an ice bath, put it into the cell disruptor, under the atmosphere of helium, the bottom of the sample is 2 cm away from the ultrasonic probe, the ultrasonic power is 55%, and the operation is performed in the mode of ultrasonic on for 2 s and off for 4 s for 10 h, and then centrifuged at 8000 rpm. 10min, freeze-drying at -30°C for 12h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (40 mg) obtained in step S1 in dimethyl sulfoxide (10 mL), the ultrasonic power is 55%, and the time is 40 minutes; then add poly-3-azide to the dispersion of black phosphorene Methyl-3, methyloxetane (2 g) was treated with mechanical stirring at 500 rpm for 2 hours to obtain a uniform black phosphorene mixed solution, and the whole process was carried out under helium gas.

S3. Place the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then introduce helium gas, repeat 3 times, and then heat it at 7°C The temperature was raised to 180°C at a rate of /min, kept for 30h, and after cooling, the mixture was centrifuged at 6000rpm for 20min, then washed three times with dimethyl sulfoxide and deionized water, and dried for 4 hours to obtain modified black phosphorus ene.

Example 6

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 4 mg/ml of BP-water solution. The beaker was placed in an ice bath, placed in a cell disrupter, and in a helium atmosphere, the bottom of the sample was 2 cm away from the ultrasonic probe, the ultrasonic power was 65%, and the ultrasonic wave was turned on for 2 s and turned off for 4 s for 12 h, and then centrifuged at 9000 rpm. 10min, freeze-drying at -20°C for 8h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (30 mg) obtained in step S1 in N-methylpyrrolidone (10 mL), the ultrasonic power is 65%, and the time is 50 minutes; then add poly3,3- Diazidomethyloxetane (2 g) was treated with mechanical stirring at 700 rpm for 3 hours to obtain a uniform black phosphorene mixed solution. The whole process was carried out under helium gas.

S3. Put the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then pass helium gas, repeat 3 times, and then at 8°C The temperature was raised to 180 °C at a rate of /min, kept for 35 h, and after cooling, the mixture was centrifuged at 8000 rpm for 25 min, washed with N-methylpyrrolidone and deionized water 4 times each, and dried for 4 hours to obtain modified black phosphorus ene.

Example 7

S1. Purge and grind the black phosphorus crystals with argon gas in a mortar to a powder with metallic luster, transfer the BP powder to a beaker filled with argon gas, add an appropriate amount of oxygen-free deionized water to the beaker, and the configuration concentration is 6 mg/ml of BP-water solution. Put the beaker in an ice bath, put it into the cell disrupter, under a helium atmosphere, the bottom of the sample is 2 cm away from the ultrasonic probe, the ultrasonic power is 85%, and the ultrasonic is turned on for 2 s and off for 4 s for 18 h, and then centrifuged at 10,000 rpm. 10min, freeze-drying at -10℃ for 11h to obtain black phosphorene;

S2, ultrasonically disperse the black phosphorene (30 mg) obtained in step S1 in polyethylene glycol (20 mL), the ultrasonic power is 95%, and the time is 100 minutes; then add 3,3-bilayer to the dispersion of black phosphorene Nitromethyl butylene oxide-tetrahydrofuran copolyether (1.8 g) was treated with mechanical stirring at 1200 rpm for 5 hours to obtain a uniform black phosphorene mixed solution. The whole process was carried out under helium gas.

S3. Put the black phosphorene mixture obtained in step S2 in a Shrek tube, first freeze it with liquid nitrogen, then use a vacuum pump to evacuate it, and then pass helium gas, repeat 3 times, and then at 4°C The temperature was raised to 200 °C at a rate of /min, kept for 50 h, and after cooling, the mixture was centrifuged at 9000 rpm for 30 min, washed with polyethylene glycol and deionized water for 6 times each, and dried for 8 hours to obtain modified black phosphorene.

The reinforcing effect of the modified black phosphorene prepared in the embodiment of the present invention is described below through specific application examples, and the reinforcing effect of the reinforcing agent is investigated through tensile property test.

Application example 1

The air-stable black phosphorene containing P=N group prepared in the above Example 1 was added to the GAP adhesive system (GAP, N100 curing agent) according to the ratio in Table 1 to prepare a reinforced GAP adhesive system. Splines, 50mm x 20mm x 4mm, were used for tensile properties testing. The test results are shown in the following table:

Table 1 Application example of the present invention enhances the effect of GAP adhesive system

It can be seen from Table 1 that the reinforcing agent of Example 1 of the present invention is added to the GAP adhesive system, and the reinforcing effect is significantly improved, and the mechanical properties also increase with the increase of the addition amount.

The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments, and the same and similar parts between the various embodiments can be referred to each other.

The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

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

s1, preparing the black phosphorus crystal into a BP-aqueous solution, and preparing the BP-aqueous solution into black phosphorus alkene;

s2, dispersing the black phosphorus alkene obtained in the step S1 in a reaction solvent to obtain a black phosphorus alkene dispersion liquid, and adding a poly-azide compound into the black phosphorus alkene dispersion liquid to obtain a black phosphorus alkene mixed liquid;

s3, carrying out heat treatment on the black phosphorus alkene mixed solution obtained in the step S2 to generate modified black phosphorus alkene;

the steps are all carried out under protective gas;

the poly azide compound is one or more of poly azide glycidyl ether, poly 3-azidomethyl-3, methyl oxetane, poly 3, 3-bis-azidomethyloxetane and 3, 3-bis-azidomethyloxetane-tetrahydrofuran copolyether;

in the step S3, during heat treatment, the temperature is raised to 100-200 ℃ at the speed of 2-10 ℃/min, and then the temperature is kept for 12-60 h.

2. The method according to claim 1, wherein in step S1, the concentration of the BP-water solution is 1-10 mg/mL.

3. The method according to claim 1 or 2, wherein in step S2, the solubility ratio of the black phosphorus alkene to the reaction solvent is 1-5 mg/mL, and the mass ratio of the black phosphorus alkene to the polyazid compound is 1: 50-70;

the reaction solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and polyethylene glycol.

4. The method according to claim 1 or 2, wherein in step S2, the polyazido compound is added and stirred to obtain a black phosphorus alkene mixture; the stirring speed is 100-1500 rpm, and the stirring time is 1-5 h.

5. The method as claimed in claim 1, wherein the shielding gas is one of nitrogen, argon, helium, neon and carbon dioxide.

6. The preparation method of the modified black phosphorus alkene as claimed in claim 1, wherein the modified black phosphorus alkene is obtained by cooling, centrifuging, washing and drying the mixture after the heat treatment;

the cooling temperature is room temperature;

the centrifugation time is 10-30 min, and the centrifugation rotating speed is 3000-10000 rpm;

washing with a reaction solvent and then washing with water;

the drying mode is one of critical point drying, supercritical drying, vacuum drying and freeze drying with carbon dioxide as medium.

7. The modified black phosphorus alkene prepared by the preparation method of the modified black phosphorus alkene in any one of the claims 1-6.

8. Use of the modified black phosphene of claim 7 in catalyst materials, electrochemical materials or aeronautical materials.

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