CN111483988A - Preparation method of antioxidant black phosphorus nanosheet - Google Patents

Preparation method of antioxidant black phosphorus nanosheet Download PDF

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CN111483988A
CN111483988A CN202010305400.9A CN202010305400A CN111483988A CN 111483988 A CN111483988 A CN 111483988A CN 202010305400 A CN202010305400 A CN 202010305400A CN 111483988 A CN111483988 A CN 111483988A
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black phosphorus
phosphorus nanosheet
nanosheet
oxidation
antioxidant
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CN111483988B (en
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翁建
陈园园
彭健
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Xiamen University
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/003—Phosphorus
    • C01B25/006—Stabilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

A preparation method of an antioxidant black phosphorus nanosheet belongs to the field of two-dimensional layered materials. The method comprises the following steps: adding the black phosphorus nanosheet into an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheet, and simultaneously preparing a halogenated alkane modification solution of alkylamine as a surface modifier; mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture; placing the mixture in a sealed system heated in inert atmosphere for reflux reaction; and cooling the mixed solution, and then carrying out liquid-solid separation, washing and drying to obtain the antioxidant black phosphorus nanosheet. Dialkyl alkyl methylamine is grafted on the surface of the black phosphorus nanosheet through a P-C-N bond, wherein P is directly connected with methylene, dialkyl amine is exposed outside, the oxidation kinetics of the alkyl amine is slow, and the oxidation of the black phosphorus nanosheet can be effectively prevented. Meanwhile, compared with the existing aromatic azide chemical, the dialkyl methylamine is low in price and environment-friendly. The method is suitable for the fields of field effect transistors, photoelectric detectors and the like.

Description

Preparation method of antioxidant black phosphorus nanosheet
Technical Field
The invention belongs to the field of two-dimensional layered materials, relates to a black phosphorus material, and particularly relates to a preparation method of an antioxidant black phosphorus nanosheet.
Background
In recent years, two-dimensional BP, as a semiconductor having a layered structure, has attracted extensive research interest from a large number of researchers. Unlike graphene, black phosphorus is a thickness-dependent moietyA conductor having a direct band from the band value of 0.3eV for bulk materials to 1.5eV for a single layer of black phospholene. Compared with molybdenum disulfide, black phosphorus has higher carrier mobility (200) -1000cm 2V-1 s-1) and larger on-off ratio (>105) And anisotropic properties. The excellent performances enable the black phosphorus to have wide application prospects in the field of nano photoelectric devices, and also have good application prospects in the fields of catalysis, sensing and intelligent equipment, particularly field effect transistors, anisotropic photoelectric detectors and the like.
Although black phosphorus possesses these excellent properties, its instability in air and water limits its application. It is well documented that black phosphorus readily reacts with oxygen and water at room temperature, causing compositional changes that degrade and degrade its optoelectronic properties (angelw. chem. int. ed,2016,128,5087). That is, the lone pair of electrons in BP readily reacts with oxygen to form phosphate, phosphite and some other PxOyTherefore, scientists adopt a series of strategies aiming at the antioxidation of the black phosphorus nanosheet, wherein the strategies mainly comprise covalent functional modification (such as P-C bond) and non-official coordination chemistry (Ti L)4) Electrostatic adsorption (PEG-NH)2) Or physical coating (alumina, graphene, boron nitride), etc. The covalent modification method can realize effective oxidation resistance of the black phosphorus due to strong interaction of the covalent modification method on the black phosphorus. At present, the passivation of the black phosphorus surface can be better realized by forming a P-C bond or a P-O-C bond on the black phosphorus surface to passivate the black phosphorus surface (Angew. chem. int. Ed.2017,56,9891). But still limited by insufficient stability, complex operation process, higher cost and the like. Therefore, there is a need for an improved technique to address the above-mentioned deficiencies.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the antioxidant black phosphorus nanosheet, which is simple in method and low in cost, can enhance the stability of the black phosphorus nanosheet by covalently grafting dialkyl methylamine onto the surface of the black phosphorus nanosheet, and does not influence the physicochemical property of the black phosphorus nanosheet.
The invention comprises the following steps:
1) adding the black phosphorus nanosheet into an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheet, and simultaneously preparing a halogenated alkane modification solution of alkylamine as a surface modifier;
2) mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture;
3) placing the mixture in a sealed system heated in inert atmosphere for reflux reaction;
4) and cooling the mixed solution, and then carrying out liquid-solid separation, washing and drying to obtain the antioxidant black phosphorus nanosheet.
In the step 1), the thickness of the black phosphorus nanosheet can be 1-100 nm; the mass ratio of the black phosphorus nanosheet to the organic solvent to the halogenated alkane can be (0.01-1): 20-1000); the organic solvent may be selected from at least one of amide-based solvents, alcohol-based solvents, and the like, and the amide-based solvents may be selected from at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and the like; the alcoholic solvent may be at least one selected from monohydric alcohol, dihydric alcohol, polyhydric alcohol, etc.; the halogenated alkane may be selected from at least one of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, dichloroethane, trichloroethane, etc.
In the step 2), the mass ratio of the surface modifier to the black phosphorus nanosheet dispersion may be (5-100): 0.01-1), and the surface modifier may be at least one selected from trimethylamine, N-diethylmethylamine, N-dimethylethylamine, triethylamine, N-diethylpropylamine, N-dipropylethylamine, tripropylamine, N-dipropylbutylamine, N-dibutylpropylamine, tributylamine, and the like.
In the step 3), a high-temperature and high-pressure resistant reaction container can be adopted for the reaction, the reaction temperature can be 20-300 ℃, and the reaction time can be 0.01-60 h; the reaction temperature is preferably 80-140 ℃, and the reaction time is 0.01-50 h.
In the step 4), dialkyl methylamine is modified on the surface of the oxidation-resistant black phosphorus nanosheet, and the dialkyl methylamine can be at least one of trimethylamine, diethyl methylamine, dipropyl methylamine, N-ethyl propyl methylamine, dibutyl methylamine and the like; the covalently grafted dialkylalkylmethylamine may be by way of a P-C-N bond.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, dialkyl alkyl methylamine is grafted on the surface of the black phosphorus nanosheet through a P-C-N bond, wherein P is directly connected with methylene, dialkyl amine is exposed outside, the alkylamine oxidation kinetics is slow, and the oxidation of the black phosphorus nanosheet can be effectively prevented. Meanwhile, compared with the aromatic azide chemical in the prior literature, the dialkyl methylamine is low in price and environment-friendly.
2. The method is suitable for the black phosphorus nanosheets prepared by various methods, can be used for the black phosphorus nanosheets with different thicknesses, sizes and stable dispersing agents, and the prepared black phosphorus can be applied to the antioxidant field effect transistor.
3. Compared with the antioxidant black phosphorus nanosheet before modification, the antioxidant black phosphorus nanosheet prepared by the method disclosed by the invention has better antioxidant capacity, has better dispersibility in polar solvents such as ethanol and the like, and can be used in the fields of electrode materials, catalytic assistants and the like.
4. The method is simple to operate and low in cost, and can realize effective antioxidant modification of the black phosphorus nanosheet.
5. Compared with the black phosphorus nanosheet which is not treated by dialkyl methylamine, the treated black phosphorus nanosheet has unchanged contact resistance, and is suitable for the fields of field effect transistors, photoelectric detectors and the like.
Drawings
FIG. 1 is a schematic flow chart according to an embodiment of the present invention.
Fig. 2 is a scanning electron microscope photograph of the oxidation-resistant black phosphorus nanosheets prepared in accordance with example 2 of the present invention.
Fig. 3 is a transmission electron microscope photograph of black phosphorus nanosheets prepared according to example 3 of the present invention, placed in air for 3 days.
Fig. 4 is a transmission electron microscope photograph of the antioxidant black phosphorus nanosheets prepared in accordance with example 3 of the present invention, placed in air for 200 days.
Fig. 5 is a graph of the uv-vis spectra of black phosphorus nanoplates and oxidation-resistant black phosphorus nanoplates prepared according to example 5 of the present invention over time.
Fig. 6 is a graph of the trend of the relative conductivity of the black phosphorus nanoplates and the oxidation-resistant black phosphorus nanoplates prepared according to example 5 of the present invention over time.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
As shown in fig. 1, an embodiment of the present invention includes the following steps:
1) preparing black phosphorus nanosheet dispersion liquid, and preparing alkylamine modification solution at the same time;
2) mixing the black phosphorus nanosheet dispersion liquid with an alkylamine modification solution to obtain a mixture;
3) the mixture is reacted under the condition of sealing and heating;
4) and (4) separating the brown solid after the reaction, washing and drying to obtain the antioxidant black phosphorus nanosheet.
Specific examples are given below.
Example 1:
step 1, preparing a black phosphorus nanosheet with the diameter of 1-100 nm, namely dispersing a BP material in an anhydrous nitrogen-nitrogen dimethyl formamide/ethanol solution with the mass concentration of 0.5mg m L-1Introducing argon for 0.5h to remove oxygen, performing ultrasonic treatment for 30h (KD250, 250W) under ice bath condition, standing overnight to remove the unexfoliated BP precipitate, centrifuging the supernatant at 12000rpm for 20min to remove nitrogen-nitrogen dimethylformamide solvent molecules, washing the precipitate with ethanol, and vacuum drying to obtain the final product, wherein 7.59g Triethylamine (TEA) is dissolved in 50m L CH2Cl2To prepare a solution of the alkylamine.
Step 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous DMF solution, adding the solution of the alkyl amine, and uniformly mixing by stirring for 1 hour.
And step 3: and sealing the mixed solution, heating to 100 ℃ under the protection of Ar, and refluxing for 12h to fully react.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging at 12000rpm for 20min to remove the solvent, centrifuging and cleaning the reaction system for several times by using acetone and ethanol, and drying in vacuum to obtain the antioxidant black phosphorus nanosheet. The flow chart of the steps can also be seen in fig. 1.
Example 2:
step 1, preparing black phosphorus nanosheets with diameters of 1-100 nm, namely dispersing BP material in anhydrous formamide/ethanol solution with mass concentration of 0.5mg m L-1Removing oxygen by introducing argon for 0.5h, performing ultrasonic treatment for 30h (KD250, 250W) under ice bath condition, standing overnight to remove un-peeled BP precipitate, centrifuging supernatant suspension at 12000rpm for 20min to remove nitrogen-nitrogen dimethylformamide solvent molecules, washing precipitate with ethanol, and vacuum drying while dissolving 9.59g Diethylmethylamine (DEMA) in 50m L CH2ClCH2A solution of the alkylamine was prepared in Cl.
Step 2, dispersing 50mg of black phosphorus nanosheets in 50m L anhydrous benzyl alcohol solution, adding the solution for preparing the alkylamine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture was heated to 140 ℃ under nitrogen blanket and refluxed for 10 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 20min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
A scanning electron micrograph of the oxidation-resistant black phosphorus nanoplates prepared in example 2 is shown in fig. 2.
Example 3:
step 1, preparing black phosphorus nanosheets with diameters of 1-100 nm, namely dispersing BP material in anhydrous N-methylpyrrolidone solution with mass concentration of 0.5mg m L-1Removing oxygen by introducing argon for 0.5h, performing ultrasonic treatment for 30h (KD250, 250W) under ice bath condition, standing overnight to remove un-peeled BP precipitate, centrifuging the supernatant at 12000rpm for 20min to remove NMP solvent molecules, washing the precipitate with ethanol, and vacuum drying to obtain a solution, wherein 7.59g Triethylamine (TEA) is dissolved in 50m L CH2Cl2To prepare a solution of the alkylamine.
And 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous DMF solution, adding the solution for preparing the alkylamine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture was heated to 90 ℃ under nitrogen and refluxed for 12 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 20min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
A transmission electron micrograph of the black phosphorus nanoplates prepared in example 3, which were left in air for 3 days, is shown in fig. 3, and it can be seen from fig. 3 that the lamellar structure of the black phosphorus was apparently destroyed to form some of the bubble-forming oxides of phosphorus. A transmission electron micrograph of the antioxidant black phosphorus nanosheet prepared in example 3, which was left in air for 200 days, is shown in fig. 4, and it can be seen from fig. 4 that the lamellar structure of the black phosphorus still remained intact.
Example 4:
step 1, preparing black phosphorus nanosheets with diameters of 1-100 nm, namely dispersing BP material in anhydrous nitrogen cyclohexyl pyrrolidone solution with mass concentration of 1mg m L-1Removing oxygen by introducing argon for 1h, performing ultrasonic treatment for 24h (KD250, 250W) under ice bath condition, standing overnight to remove un-stripped BP precipitate, centrifuging supernatant suspension at 12000rpm for 30min to remove azocyclohexylpyrrolidone solvent molecules, washing precipitate with ethanol, and vacuum drying to obtain a solution containing 8.39g of diethylpropylamine dissolved in 50m of L CH2Cl2To prepare a solution of the alkylamine.
And 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous DMF solution, adding the solution for preparing the alkylamine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture is heated to 80 ℃ under the protection of Ar and refluxed for 12 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 20min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
Example 5:
step 1, preparing black phosphorus nanosheets with diameters of 1-100 nm, namely dispersing BP material in ether solution with mass concentration of 1mg m L-1Removing oxygen by introducing argon for 1h, ultrasonically treating for 48h (KD250, 250W) under ice bath conditions, standing overnight to remove the unexfoliated BP precipitate, centrifuging the upper suspension at 12000rpm for 30min to remove ether solvent molecules, washing the precipitate with ethanol, and performing vacuum drying, wherein 12.28g of tripropylamine is dissolved in 50m L of trichloromethane to prepare a solution of the alkylamine.
And 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous formamide solution, adding the solution for preparing the alkylamine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture is heated to 130 ℃ under the protection of Ar and refluxed for 12 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 20min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
The ultraviolet-visible spectrum change curves of the black phosphorus nanosheet prepared in example 5 and the antioxidant black phosphorus nanosheet are shown in fig. 5, and it can be seen from fig. 5 that the relative intensity of the characteristic peak of the black phosphorus nanosheet at 465nm is obviously reduced with time, which indicates that the black phosphorus is obviously oxidized in the air; the relative intensity of the characteristic peak of the antioxidant black phosphorus nanosheet at 465nm basically maintains stable along with time, and can be maintained to 87% of the original intensity even after 200 days of air exposure, which shows that the modified black phosphorus nanosheet can effectively resist oxidation. The trend graph of the relative conductivity of the black phosphorus nanoplates prepared in example 5 and the antioxidant black phosphorus nanoplates as a function of time is shown in fig. 6. Similarly, the conductivity of the black phosphorus nanosheet without being subjected to the antioxidant treatment sharply decreases with time, indicating that the nanosheet has been significantly oxidized; and after the alkylamine anti-oxidation treatment, the conductivity is maintained stable, and the conductivity can be maintained to be more than 80% of the original conductivity even under the air exposure condition of 2 months, so that the modification treatment of the invention can really realize the effective anti-oxidation of the black phosphorus nanosheet.
Example 6:
step 1, preparing black phosphorus nanosheets with diameters of 1-100 nm, namely dispersing BP material in nitrogen-nitrogen dimethylformamide solution with mass concentration of 1mg m L-1Introducing argon for 1h to remove oxygen, and performing ultra-high pressure treatment under ice bath condition24h (KD250, 250W) standing overnight to remove the un-stripped BP precipitate, centrifuging the supernatant at 12000rpm for 30min to remove the nitrogen-nitrogen dimethylformamide molecule, washing the precipitate with ethanol, and vacuum drying while dissolving 8.39g diethylpropylamine in 50m L chloroform to prepare a solution of the alkylamine.
And 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous nitrogen-nitrogen dimethylformamide solution, adding the solution for preparing the alkyl amine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture is heated to 80 ℃ under the protection of Ar and refluxed for 12 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 30min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
Example 7:
step 1, preparing a black phosphorus nanosheet with the diameter of 1-100 nm, namely dispersing a BP material in a nitrogen-nitrogen dimethyl formamide solution with the mass concentration of 0.5mg m L-1Argon is introduced for 0.5h to remove oxygen, ultrasonic treatment is carried out for 30h (KD250, 250W) under ice bath conditions, standing overnight is carried out to remove the BP precipitate which is not stripped, the upper layer suspension is centrifuged at 12000rpm for 30min to remove nitrogen and nitrogen dimethyl formamide molecules, the precipitate is washed by ethanol and dried in vacuum, and at the same time, 12.46g of dipropyl butylamine is dissolved in 50m L of chloroform to prepare the solution of the alkyl amine.
And 2, dispersing 50mg of black phosphorus nanosheets in 50m L of anhydrous nitrogen-nitrogen dimethylformamide solution, adding the solution for preparing the alkyl amine, and ultrasonically mixing uniformly for 1 hour.
And step 3: the mixture is heated to 80 ℃ under the protection of Ar and refluxed for 12 h.
And 4, step 4: and cooling the reaction system to room temperature, centrifuging the obtained dispersion liquid at 12000rpm for 30min to remove the solvent, centrifuging and cleaning the dispersion liquid for several times by using acetone and ethanol, and drying the dispersion liquid in vacuum to obtain the antioxidant black phosphorus nanosheet.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.

Claims (10)

1. A preparation method of an antioxidant black phosphorus nanosheet is characterized by comprising the following steps:
1) adding the black phosphorus nanosheet into an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheet, and simultaneously preparing a halogenated alkane modification solution of alkylamine as a surface modifier;
2) mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture;
3) placing the mixture in a sealed system heated in inert atmosphere for reflux reaction;
4) and cooling the mixed solution, and then carrying out liquid-solid separation, washing and drying to obtain the antioxidant black phosphorus nanosheet.
2. The preparation method of the oxidation-resistant black phosphorus nanosheet, according to claim 1, wherein in step 1), the thickness of the black phosphorus nanosheet is 1-100 nm.
3. The method for preparing an antioxidant black phosphorus nanosheet of claim 1, wherein in step 1), the mass ratio of the black phosphorus nanosheet, the organic solvent and the haloalkane is (0.01-1): 20-1000).
4. The method for preparing oxidation-resistant black phosphorus nanosheets according to claim 1, wherein in step 1), the organic solvent is at least one selected from the group consisting of amide solvents and alcohol solvents, wherein the amide solvents are at least one selected from the group consisting of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide and diethylacetamide; the alcoholic solvent may be at least one selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol.
5. A method for preparing oxidation-resistant black phosphorus nanoplate as claimed in claim 1, wherein in step 1), the halogenated alkane is selected from at least one of methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, dichloroethane and trichloroethane.
6. The method for preparing oxidation-resistant black phosphorus nanosheet, according to claim 1, wherein in step 2), the mass ratio of the surface modifier to the black phosphorus nanosheet dispersion is (5-100): 0.01-1.
7. A method for preparing oxidation-resistant black phosphorus nanosheets as recited in claim 1 in step 2), wherein the surface modifier is selected from at least one of trimethylamine, N, -diethylmethylamine, N, -dimethylethylamine, triethylamine, N, -diethylpropylamine, N, -dipropylethylamine, tripropylamine, N, -dipropylbutylamine, N, -dibutylpropylamine, and tributylamine.
8. The preparation method of the antioxidant black phosphorus nanosheet, according to claim 1, characterized in that in step 3), a high-temperature and high-pressure resistant reaction vessel is adopted for the reaction, the reaction temperature is 20-300 ℃, and the reaction time is 0.01-60 h; the reaction temperature is preferably 80-140 ℃, and the reaction time is 0.01-50 h.
9. The method for preparing oxidation-resistant black phosphorus nanosheets of claim 1, wherein in step 4), the surface of the oxidation-resistant black phosphorus nanosheets is modified with dialkyl methylamine; the dialkylalkylmethylamines can be covalently grafted by means of a P-C-N bond.
10. A method for preparing an oxidation-resistant black phosphorus nanosheet, as recited in claim 9, wherein the dialkylmethylamine is at least one of trimethylamine, diethylmethylamine, dipropylmethylamine, N-ethylpropylmethylamine, and dibutylmethylamine.
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CN111847408A (en) * 2020-08-12 2020-10-30 中国药科大学 Two-dimensional black phosphorus surface protection method
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CN113134092A (en) * 2021-03-10 2021-07-20 中山大学·深圳 Black phosphorus material and preparation method and application thereof
CN113388308A (en) * 2021-05-17 2021-09-14 昆明理工大学 Epoxy resin anticorrosive flame-retardant coating and preparation method thereof
CN113912030A (en) * 2021-11-23 2022-01-11 北京理工大学 Modified black phosphorus alkene, and preparation method and application thereof
CN114345408A (en) * 2021-12-04 2022-04-15 湖北兴发化工集团股份有限公司 Black phosphorus supported palladium nanoparticle composite material and preparation method thereof
CN114369334A (en) * 2022-01-11 2022-04-19 广东和润新材料股份有限公司 Preparation method of novel phosphorus-nitrogen flame retardant

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CN111847408A (en) * 2020-08-12 2020-10-30 中国药科大学 Two-dimensional black phosphorus surface protection method
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CN113134092A (en) * 2021-03-10 2021-07-20 中山大学·深圳 Black phosphorus material and preparation method and application thereof
CN113388308A (en) * 2021-05-17 2021-09-14 昆明理工大学 Epoxy resin anticorrosive flame-retardant coating and preparation method thereof
CN113912030A (en) * 2021-11-23 2022-01-11 北京理工大学 Modified black phosphorus alkene, and preparation method and application thereof
CN114345408A (en) * 2021-12-04 2022-04-15 湖北兴发化工集团股份有限公司 Black phosphorus supported palladium nanoparticle composite material and preparation method thereof
CN114369334A (en) * 2022-01-11 2022-04-19 广东和润新材料股份有限公司 Preparation method of novel phosphorus-nitrogen flame retardant
CN114369334B (en) * 2022-01-11 2024-01-23 广东和润新材料股份有限公司 Preparation method of phosphorus-nitrogen flame retardant

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