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CN-118515247-B - High-stability organophosphorus functionalized black phosphorus nanosheet dispersion liquid and preparation method thereof

CN118515247BCN 118515247 BCN118515247 BCN 118515247BCN-118515247-B

Abstract

The invention relates to a high-stability organophosphorus functionalized black phosphorus nano-sheet dispersion liquid and a preparation method thereof, wherein the organophosphorus functionalized black phosphorus nano-sheet dispersion liquid comprises organophosphorus functionalized black phosphorus nano-sheets and a low-boiling point organic solvent, the solid content of the organophosphorus functionalized black phosphorus nano-sheets in the low-boiling point organic solvent is 0.20-0.50 mg/mL, the organophosphorus functionalized black phosphorus nano-sheets are of a lamellar structure, the average thickness is 1.56-2.21 nm, the average number of layers is 3-5, and the organophosphorus functionalized black phosphorus nano-sheets are black phosphorus nano-sheets with surface modified organic phosphonic acids and ammonium salts thereof. The organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid is prepared by adopting a mechanical ball milling-liquid phase ultrasonic coupling method, and the obtained high-stability organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid has good storage stability under the condition of keeping high solid content in a low-boiling point solvent, can be stably stored in air for more than 16 days, and can be stored in nitrogen atmosphere for more than 27 days.

Inventors

  • LIU SHUMEI
  • Zheng yongjia
  • ZHAO JIANQING
  • YUAN YANCHAO

Assignees

  • 华南理工大学

Dates

Publication Date
20260512
Application Date
20240511

Claims (7)

  1. 1. The high-stability organophosphorus functionalized black phosphorus nano sheet dispersion liquid is characterized by comprising organophosphorus functionalized black phosphorus nano sheets and a low-boiling point organic solvent, wherein the solid content of the organophosphorus functionalized black phosphorus nano sheets in the low-boiling point organic solvent is 0.20-0.50 mg/mL, the organophosphorus functionalized black phosphorus nano sheets are of a lamellar structure, the average thickness is 1.56-2.21 nm, the average number of layers is 3-5, and the organophosphorus functionalized black phosphorus nano sheets are black phosphorus nano sheets with surface modified organic phosphonic acid and ammonium salts thereof; The organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid is obtained by dissolving organic phosphonic acid in a low-boiling point organic solvent, adding amino black phosphorus nano-sheets, performing ultrasonic dispersion, and performing centrifugal separation on the obtained suspension liquid to remove solid matters after the ultrasonic dispersion is finished; the aminated black phosphorus nanosheets are obtained by mechanically ball-milling the ground black phosphorus crystals with nitrogen-containing auxiliary agents and ball-milling beads in inert atmosphere; the organic phosphonic acid is selected from one or more of phenylphosphonic acid, phytic acid, methylphosphonic acid and propylphosphonic acid; the low boiling point organic solvent is an organic solvent having a boiling point below 100 ℃; The nitrogen-containing auxiliary agent is selected from one or more of diisopropanolamine, hexamethylenediamine, adipic acid hexamethylenediamine salt and tetraethylammonium sulfate; The mass ratio of the aminated black phosphorus nano-sheet to the organic phosphonic acid is 1:0.5-2.5, wherein the dosage of the organic phosphonic acid is 0.05-0.25 g per 100mL of low-boiling point organic solvent; the mass ratio of the black phosphorus crystal to the nitrogen-containing auxiliary agent to the ball-milling beads is 1 (4-6) to 50-80.
  2. 2. The high stability organophosphorus functionalized black phosphorus nanoplatelet dispersion of claim 1, wherein the organophosphorus functionalized black phosphorus nanoplatelet dispersion has a shelf life of at least 9 days in air and at least 16 days in nitrogen atmosphere.
  3. 3. The high-stability organophosphorus functionalized black phosphorus nanosheet dispersion liquid according to claim 1, wherein the ball-milling beads are stainless steel balls, and the low-boiling point organic solvent is one or more selected from absolute ethyl alcohol, methanol, acetone and butanone.
  4. 4. A method for preparing the high-stability organophosphorus functionalized black phosphorus nanoplatelet dispersion according to any of claims 1-3, comprising the steps of: (1) Mechanically ball-milling the ground black phosphorus crystal, the nitrogen-containing auxiliary agent and ball-milling beads in an inert atmosphere, cooling to room temperature, sieving, washing and drying to obtain the black phosphorus amide nanosheets; (2) The preparation method of the organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid comprises the steps of dissolving organic phosphonic acid in a low-boiling-point organic solvent, adding the aminated black phosphorus nano-sheets, performing ultrasonic dispersion, and after the ultrasonic dispersion is finished, performing centrifugal separation on the obtained suspension liquid to remove solid matters, thereby obtaining supernatant liquid, namely the organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid.
  5. 5. The method for preparing the high-stability organophosphorus functionalized black phosphorus nanoplatelet dispersion according to claim 4, wherein the grinding in the step (1) is performed in a glove box with inert atmosphere, and black phosphorus crystals are ground in a mortar for 20-40 min; the inert atmosphere in the step (1) is helium, nitrogen or argon; the mechanical ball milling is carried out after being packaged in a ball milling tank in a glove box containing inert atmosphere, the mechanical ball milling procedure is carried out at room temperature at the rotating speed of 500-800 r/min, one-way ball milling is carried out for 30+/-3 min, the stopping time is 6+/-3 min, the total ball milling is carried out for 41-45 cycles, the total time is 22-28 h, the washing mode in the step (1) is centrifugal washing, the centrifugal washing is washing a product with deionized water, and after centrifugal separation, Taking a sedimentation product, and performing the process for 3-6 times, wherein the centrifugal condition is that the rotating speed is 9000-12000 r/min, and the single centrifugal time is 6-10 min; And (3) drying in the step (1) in vacuum, and placing the product in a vacuum oven with the set temperature of 50-75 ℃ for drying for 8-12 hours to obtain the gray black powder which is the aminated black phosphorus nano-sheet.
  6. 6. The method for preparing the high-stability organophosphorus functionalized black phosphorus nanosheet dispersion liquid according to claim 4, wherein in the step (2), ultrasonic dispersion is carried out at a temperature of 10-35 ℃ under the protection of inert gas in the absence of light, the ultrasonic power is 400-600W, and the ultrasonic time is 4-6 h; And (3) centrifuging the suspension in the step (2) at a rotating speed of 2000-4000 r/min for 5-12 min.
  7. 7. The method for preparing the high-stability organophosphorus functionalized black phosphorus nanosheet dispersion liquid according to claim 6, wherein the light shielding step is to wrap a blue cap bottle mixed with the low-boiling point organic solvent dispersion liquid of the aminated black phosphorus nanosheets and the organic phosphonic acid with tin paper, and cap a top cap of an ultrasonic instrument, and the inert gas is helium, nitrogen or argon.

Description

High-stability organophosphorus functionalized black phosphorus nanosheet dispersion liquid and preparation method thereof Technical Field The invention relates to the field of preparation of two-dimensional nano materials, in particular to high-stability organic phosphorus functionalized black phosphorus nano sheet dispersion liquid and a preparation method thereof. Background As an emerging two-dimensional nano material, the Black Phosphorus (BP) nano-sheet has wide prospects in the fields of energy storage equipment, catalysts, sensors, biomedical equipment and the like. The black phosphorus nano-sheet dispersion liquid has the advantages of convenient application, easy large-scale preparation and the like, but the dispersion medium has larger influence on the storage stability. Currently, organic solvents with boiling points above 150 ℃ such as N, N-dimethylformamide (DMF, 153 ℃) and dimethyl sulfoxide (DMSO, 189 ℃) and N-methylpyrrolidone (NMP, 203 ℃) are mostly used as dispersion media for black phosphorus nanoplatelet dispersions, and Hansen (Hansen) solubility parameters (an index for evaluating the compatibility between nanomaterials and organic solvents) of these high boiling organic solvents are relatively close to those of black phosphorus nanoplatelets. Chinese patent No. 201910862043.3 discloses a method for stripping high-quality and few-layer black phosphorus nano-sheets from N, N-dimethylformamide by means of liquid phase ultrasonic. However, the solvent is required to be removed in the application, the removal of the high-boiling point solvent is difficult, the low-boiling point solvent (such as absolute ethyl alcohol, acetone, butanone and the like, wherein the absolute ethyl alcohol has the highest boiling point of 78.5 ℃) and has the advantages of easy removal, less residue and the like, the application meaning of dispersing the black phosphorus nano-sheets in the low-boiling point solvent to form stable dispersion liquid is greater, and the black phosphorus nano-sheets are difficult to form stable black phosphorus nano-sheet dispersion liquid particularly in the application occasions of photothermal treatment, batteries, electronic devices and the like when the use temperature is not too high, but the hansen solubility parameters of the black phosphorus nano-sheets and the low-boiling point solvent are not matched. The invention of China patent No. CN201610680032.X discloses a black phosphorus nano-sheet and a preparation method and application thereof, wherein the preparation method is to place black phosphorus powder in anaerobic water, control the black phosphorus powder to be alkaline, carry out ultrasonic treatment under an inert environment, and carry out centrifugal treatment on the obtained mixed solution to collect supernatant, thus obtaining black phosphorus nano-sheet dispersion liquid with solid content of 0.15mg/mL, wherein the average thickness of the black phosphorus nano-sheet is 10nm (about 20 layers) and the transverse dimension is 250nm, the dispersion liquid can be stored for 3 days under an air atmosphere and can be stably stored for 7 days under a nitrogen atmosphere, and the method avoids the use of organic solvents, but the storage time is shorter under the condition of lower solid content. The black phosphorus nano-sheets are prepared by adopting the ultrasonic method, and the ultrasonic method weakens the interaction between the nano-sheets by ultrasonic cavitation in a liquid phase system to realize stripping, and the obtained black phosphorus nano-sheets are uneven in size and larger in thickness due to the change of the intensity of a cavitation area caused by uneven ultrasonic distribution, so that the dispersion liquid is low in solid content and poor in stability. There is still a lack of efficient methods to obtain black phosphorus nanoplatelet dispersions with high solids content and higher stability in low boiling solvents. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides the high-stability organophosphorus functionalized black phosphorus nano-sheet dispersion liquid, which can keep high solid content in a low-boiling-point solvent and has good storage stability. The organic phosphorus functionalized black phosphorus nano-sheet dispersion liquid has good storage stability under nitrogen or air atmosphere. The invention also provides a preparation method of the organophosphorus functionalized black phosphorus nanosheet dispersion liquid, wherein the preparation method is a mechanical ball milling-liquid phase ultrasonic coupling method, and can realize large-scale and high-efficiency preparation of high-solid-content dispersion of the black phosphorus nanosheets in a low-boiling-point solvent. The invention aims at realizing the following technical scheme: In a first aspect, a high-stability organophosphorus functionalized black phosphorus nanosheet dispersion is provided, the organophosphorus functionaliz