CN115108539A - Preparation and application of super-hydrophobic black phosphorus nanoparticles - Google Patents
Preparation and application of super-hydrophobic black phosphorus nanoparticles Download PDFInfo
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- C01B25/02—Preparation of phosphorus
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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Abstract
The invention belongs to the field of black phosphorus materials, and particularly relates to preparation and application of super-hydrophobic black phosphorus nanoparticles. The super-hydrophobic black phosphorus nano-particles are a super-hydrophobic black phosphorus nano-material obtained by ball-milling and stripping red phosphorus and modifying the red phosphorus with an electrophilic reagent. The preparation method comprises the following steps: putting high-purity red phosphorus and steel balls into a steel tank, adding an electrophilic reagent, and performing ball milling for 7-10 hours in an inert atmosphere. The halohydrocarbon is adopted to modify the black phosphorus nano-particles, and the black phosphorus quantum dots are further prepared, so that on one hand, the oxidation resistance of the black phosphorus material is improved, and on the other hand, the black phosphorus material is endowed with new functions of water resistance, self-cleaning, oil-water separation and the like, and can be applied to more fields.
Description
Technical Field
The invention belongs to the field of black phosphorus materials, and particularly relates to preparation and application of super-hydrophobic black phosphorus nanoparticles.
Background
In recent years, black phosphorus having a two-dimensional layered structure like graphene exhibits excellent electrical and optical characteristics while having good bioactivity and biocompatibility. However, the instability of black phosphorus and its hydrophilicity have limited its intensive research and application to some extent.
Hydrophilicity is the property of being wetted by moisture on the surface of a material. Is an interfacial phenomenon, and the essence of the wetting process is the change in the nature and energy of the material interface. When the cohesion between water molecules is less than the mutual attraction between the water molecules and the molecules of the solid material, the material is wetted by water, and the material is hydrophilic and is called hydrophilic material; when the cohesive force between water molecules is larger than the attractive force between the water molecules and the material molecules, the surface of the material cannot be wetted by water, and the material is hydrophobic (or called hydrophobic), and is called as a hydrophobic material. The hydrophilicity of black phosphorus has a significant impact on its own performance.
The poor stability of black phosphorus is due to the fact that in the honeycomb structure, after the phosphorus atom is bonded with other 3 phosphorus atoms, a pair of lone-pair electrons still exist, and the lone-pair electrons are easily abstracted by oxygen molecules, so that the oxidation of the black phosphorus on the outer layer is caused. In order to realize the stability enhancement and performance optimization of black phosphorus, researchers have developed a series of interface regulation and control technologies, such as organic coating, chemical coordination, covalent modification, ion doping, defect repair, and the like. Patent CN201610729312.5 proposes a method for coating black phosphorus with polymer to achieve the stability of black phosphorus. According to the method, a layer of organic matter is coated on the outer layer of the black phosphorus to isolate water and oxygen and slow down the degradation of the black phosphorus, however, although the method for preparing the protective layer plays a role in protection by isolating air and water, lone pair electrons of phosphorus atoms still exist, and the possibility of oxidation still exists. By a surface chemical modification method, lone-pair electrons of the black phosphorus form a coordination bond or a covalent bond to block the reaction with oxygen, so that the problem of the stability of the black phosphorus can be fundamentally solved. Patent 201510956724.8 discloses a titanium benzene sulfonate ligand (TiL4), which can coordinate with lone pair of electrons of black phosphorus by using the empty orbit of titanium atom and the strong electron-withdrawing effect of benzene sulfonate; the lone pair of electrons of the phosphorus atom is occupied after the formation of the coordinate bond and thus no longer reacts with oxygen, however, these methods fail to achieve a change in the wettability of black phosphorus.
At present, the hydrophobic modification of black phosphorus is less researched, and the hydrophobic modification of black phosphorus improves the stability of black phosphorus in a water-oxygen environment, improves the surface wettability of black phosphorus, and expands the characteristics of water resistance, oil-water separation, self-cleaning and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of super-hydrophobic black phosphorus nanoparticles aiming at the defects of the prior art, and the super-hydrophobic black phosphorus nanoparticles have excellent stability, simple preparation process and low price.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention firstly provides a super-hydrophobic black phosphorus nano-particle which is a super-hydrophobic black phosphorus nano-material obtained by ball-milling and stripping red phosphorus and modifying the red phosphorus by an electrophilic reagent.
Specifically, the electrophilic reagent is halogenated hydrocarbon, the structure of the halogenated hydrocarbon is phenyl or a substituent of C1-6 alkyl by 1-14 independent halogen atoms, and the halogen atoms comprise one or more of fluorine, chlorine, bromine and iodine.
The invention also provides a preparation method of the super-hydrophobic black phosphorus nano-particles, which comprises the steps of putting high-purity red phosphorus and a steel ball into a steel tank, simultaneously adding an electrophilic reagent, and carrying out ball milling for 7-10h in an inert atmosphere. The high-purity red phosphorus is powder with the purity of 99.999 percent.
Specifically, the mass ratio of the steel balls to the high-purity red phosphorus is 30: 1.
Specifically, the molar ratio of the high-purity red phosphorus to the electrophilic reagent is 5: 1-1: 5.
specifically, the ball milling rotating speed is 700-.
Specifically, the prepared black phosphorus nanoparticles are nanoparticles with the particle size of 30-80 nm.
The third invention provides a preparation method of the super-hydrophobic black phosphorus quantum dot, which is characterized in that the super-hydrophobic black phosphorus nano-particles are subjected to probe ultrasonic treatment for 6-10h by using a probe of 40-80kHz in an ice bath by using NMP as a solvent to obtain the super-hydrophobic black phosphorus quantum dot.
Preferably, the prepared black phosphorus quantum dots are black phosphorus nanoparticles with hydrated particle size of less than 10 nm.
The invention also provides the application of the super-hydrophobic black phosphorus nanoparticles or the super-hydrophobic black phosphorus quantum dots prepared by the preparation method in photodynamic therapy reagents or photothermal therapy reagents; in particular to the application in preparing a photo-thermal therapeutic agent for treating cancer.
The term "photodynamic therapy agent" refers to a material having a photodynamic effect. The process of the photodynamic effect is that the photosensitizer is excited by the laser irradiation with specific wavelength so as to transfer energy to the surrounding oxygen, generate singlet oxygen with strong activity, generate the cytotoxic effect and further cause the cell damage and even death;
the photothermal therapeutic agent is a material for photothermal therapy, which has high photothermal conversion efficiency, can be concentrated near tumor tissues, and can convert light energy into heat energy under the irradiation of an external light source to perform treatments such as killing cancer cells.
The design idea of the invention is as follows: because each phosphorus atom of the black phosphorus has lone pair electrons which are nucleophilic substances, and the halogenated hydrocarbon is electrophilic substances and is easy to generate electrophilic substitution reaction with the black phosphorus, the hydrocarbon chain segment is successfully modified to the surface of the black phosphorus after the halogen atom leaves, so that the conversion from hydrophilicity to hydrophobicity is realized. The reaction mechanism is as follows:
the above X is a halogen atom.
Compared with the prior art, the invention has the following outstanding effects:
1. according to the invention, the halogenated hydrocarbon is used for modifying black phosphorus nanoparticles, the hydrocarbon chain is modified on the black phosphorus, lone pair electrons of the black phosphorus form covalent bonds, and the reaction of the lone pair electrons with oxygen is blocked, so that the problem of the stability of the black phosphorus can be fundamentally solved; the technical scheme is surface modification, and the inherent properties of black phosphorus are not changed;
2. the invention has the advantages of simple and easily obtained raw materials, simple operation of production process, high yield and good reproducibility, and can realize low-cost large-scale production;
3. according to the invention, the halogenated hydrocarbon is adopted to modify the black phosphorus nanoparticles, and the black phosphorus quantum dots are further prepared, so that on one hand, the oxidation resistance of the black phosphorus material is improved, and on the other hand, new functions of water resistance, self-cleaning, oil-water separation and the like are given to the black phosphorus material, and the black phosphorus material can be applied to more fields.
Drawings
FIG. 1 is an SEM electron micrograph of the super-hydrophobic black phosphorus nanoparticles obtained in example 1;
FIG. 2 is a TEM image of the super-hydrophobic black phosphorus quantum dot obtained in example 4;
FIG. 3 is an XRD pattern of the super-hydrophobic black phosphorus nanoparticles obtained in example 1;
FIG. 4 is a cell photothermal therapy of the super-hydrophobic black phosphorus nanoparticles obtained in example 1;
fig. 5 shows cell survival rates of the superhydrophobic black phosphorus nanoparticles obtained in example 1 and the superhydrophobic black phosphorus quantum dots obtained in example 4 after photothermal therapy.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the invention.
Example 1 preparation of super-hydrophobic black phosphorus nanoparticles
Putting high-purity red phosphorus and steel balls into 50cm 3 In the steel tank, the ratio of the steel balls to red phosphorus is 30: 1. Adding a certain amount of chlorohexane at the same time, and performing ball milling in an inert atmosphere(argon) was carried out for 7 hours at a rotation speed of 700 r/min. The molar ratio of the high-purity red phosphorus to the chlorohexane is 5: 1.
example 2 preparation of super-hydrophobic black phosphorus nanoparticles
Putting high-purity red phosphorus and steel balls into 50cm 3 In the steel tank, the ratio of the steel balls to red phosphorus is 30: 1. Simultaneously adding a certain amount of bromotridecane, and performing ball milling for 10 hours in an inert atmosphere (argon), wherein the rotating speed is 1500 r/min. The molar ratio of the high-purity red phosphorus to the chlorohexane is 1: 5.
example 3 preparation of super-hydrophobic black phosphorus nanoparticles
Putting high-purity red phosphorus and steel balls into 50cm 3 In the steel tank, the ratio of the steel balls to red phosphorus is 30: 1. Simultaneously adding a certain amount of bromotridecane, and performing ball milling for 8 hours in an inert atmosphere (argon), wherein the rotating speed is 1500 r/min. The molar ratio of the high-purity red phosphorus to the chlorohexane is 1: 1.
example 4 preparation of super-hydrophobic black phosphorus quantum dots
And (3) performing probe ultrasonic treatment on the super-hydrophobic black phosphorus nanoparticles obtained in the example 1 for 10 hours by using a 40kHz probe under ice bath by using NMP as a solvent to obtain the super-hydrophobic black phosphorus quantum dots.
Example 5 preparation of super hydrophobic black phosphorus quantum dots
And (3) performing probe ultrasonic treatment on the super-hydrophobic black phosphorus nanoparticles obtained in the example 2 for 6 hours by using a 70kHz probe under ice bath by using NMP as a solvent to obtain the super-hydrophobic black phosphorus quantum dots.
Example 6 preparation of super-hydrophobic black phosphorus quantum dots
And (3) performing probe ultrasonic treatment on the super-hydrophobic black phosphorus nanoparticles obtained in the example 3 for 7 hours by using an 80kHz probe under ice bath by using NMP as a solvent to obtain the super-hydrophobic black phosphorus quantum dots.
Structural and performance testing
The super-hydrophobic black phosphorus nanoparticles prepared in examples 1 to 3 are characterized, peaks in an XRD spectrogram belong to black phosphorus crystal faces such as (020), (021), (040) and (111), the black phosphorus structures are determined, the shapes of the black phosphorus nanoparticles on the surfaces of SEM, TEM and the like are particles, and the shape characteristics of example 1 are shown in figures 1, 2 and 3.
The black phosphorus nanoparticles and the quantum dots are dispersed in ethanol and coated on a substrate to form a coating, and a water contact angle tester is used for testing a water contact angle. The super-hydrophobic black phosphorus nanoparticles prepared in examples 1 to 3 and the super-hydrophobic black phosphorus quantum dots prepared in examples 4 to 6 were subjected to a water contact angle tester for water contact angle test: are all between the water contact angle of 150 degrees and 165 degrees.
Stability tests were performed on the superhydrophobic black phosphorus nanoparticles prepared in examples 1-3 and the superhydrophobic black phosphorus quantum dots prepared in examples 4-6: observing the degradation condition of the super-hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots in the aqueous solution to detect the stability of the super-hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots, wherein the hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots are not degraded in the aqueous solution for 7 days after detection; the degradation condition of the super-hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots in the aqueous solution is observed to detect the stability of the super-hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots, and the shapes of the super-hydrophobic black phosphorus nanoparticles and the super-hydrophobic black phosphorus quantum dots are unchanged in the air for 7 days through detection, namely, obvious oxidation does not occur.
In addition, the prepared black phosphorus nanoparticles and quantum dots can be placed in an oxygen-water environment for 7 days without degradation, have high photo-thermal conversion efficiency, and can be rapidly heated to 60 ℃ within minutes under the irradiation of near infrared light, so that the photo-thermal anti-tumor effect is realized.
Example 7
The purpose of laser irradiation treatment of the superhydrophobic black phosphorus nanoparticles prepared in examples 1-3 and the superhydrophobic black phosphorus quantum dots prepared in examples 4-6 is to convert light energy into heat energy by black phosphorus, increase the temperature of the material, and further kill tumor cells. In the step of performing laser irradiation treatment, the laser irradiation is performed under the conditions that the laser wavelength is 808-810 nm, the power is 1-2W/cm, and the laser irradiation time is 5-20 minutes. The temperature of the first tumor obtained in the organism is ensured to be about 50 ℃, if the temperature is too high, other tissues of the organism can be damaged, and if the temperature is too low, the aim of killing tumor cells can not be achieved.
Example 8
Testing of the super-hydrophobic black phosphorus nanoparticles prepared in examples 1-3 and the super-hydrophobic black prepared in examples 4-6The photothermal treatment effect of the phosphorus quantum dot on tumor cells is detected by adopting a CCK-8 method to detect the cell survival rate, and the method comprises the following specific steps: the logarithmic growth of breast cancer cells (MCF7) was digested with trypsin (1:250) from the flask to prepare a cell suspension, and the cell density was adjusted to 5X 10 4 cells/mL. 1mL of cell suspension per well was added to a 12-well plate containing 5% volume fraction of CO 2 In an incubator, the culture is carried out in a static way at 37 ℃. When the cell monolayer was spread to the bottom of the 24-well plate, a PBS solution of super-hydrophobic black phosphorus (20ppm) was added, using PBS as a blank control. After standing culture for 4 hours in an incubator, the 24-well plate was placed under the laser irradiation condition of example 7 at a laser intensity of 1W/cm 2 Irradiating for 10 min. The apoptosis condition of cells is observed under a microscope, the result shows that the cells in the blank control group survive, and the cells in the group holes added with 20ppm of the super-hydrophobic black phosphorus nano-particles and the super-hydrophobic black phosphorus quantum dots are basically and completely killed, which shows that the super-hydrophobic black phosphorus nano-particles and the super-hydrophobic black phosphorus quantum dots have excellent photo-thermal anti-tumor performance, as shown in fig. 4 and 5.
Claims (10)
1. The super-hydrophobic black phosphorus nanoparticle is characterized in that red phosphorus is subjected to ball milling stripping while the red phosphorus is modified by an electrophilic reagent to obtain the super-hydrophobic black phosphorus nanoparticle.
2. The super-hydrophobic black phosphorus nanoparticle according to claim 1, wherein the electrophile is a halohydrocarbon, and the halohydrocarbon structure is phenyl or a C1-6 alkyl substituted by 1-14 independent halogen atoms, and the halogen atoms comprise one or more of fluorine, chlorine, bromine and iodine.
3. A preparation method of super-hydrophobic black phosphorus nanoparticles is characterized by placing high-purity red phosphorus and steel balls into a steel tank, adding an electrophilic reagent, and carrying out ball milling for 7-10h in an inert atmosphere.
4. The method for preparing the super-hydrophobic black phosphorus nanoparticles as claimed in claim 3, wherein the mass ratio of the steel balls to the high-purity red phosphorus is 30: 1.
5. The method for preparing the super-hydrophobic black phosphorus nanoparticles according to claim 3, wherein the molar ratio of the high-purity red phosphorus to the electrophile is 5: 1-1: 5.
6. the preparation method of the super-hydrophobic black phosphorus nanoparticles as claimed in claim 3, wherein the ball milling rotation speed is 700-1500 r/min.
7. The method for preparing the super-hydrophobic black phosphorus nanoparticles as claimed in claim 3, wherein the prepared black phosphorus nanoparticles are nanoparticles with a particle size of 30-80 nm.
8. The preparation method of the super-hydrophobic black phosphorus quantum dot is characterized in that probe ultrasonic treatment is carried out on super-hydrophobic black phosphorus nanoparticles, NMP is used as a solvent, and the super-hydrophobic black phosphorus quantum dot is obtained by ultrasonic treatment for 6-10 hours with a 40-80kHz probe under ice bath.
9. The preparation method of the super-hydrophobic black phosphorus quantum dot according to claim 8, wherein the prepared black phosphorus quantum dot is a black phosphorus nanoparticle with a hydrated particle size of less than 10 nm.
10. Use of the superhydrophobic black phosphorus nanoparticles of any one of claims 1-2 or the superhydrophobic black phosphorus nanoparticles prepared by the preparation method of any one of claims 3-7 or the superhydrophobic black phosphorus quantum dots prepared by the preparation method of any one of claims 8-9 in photodynamic therapy reagents or photothermal therapy reagents; in particular to the application in preparing a photo-thermal therapeutic agent for treating cancer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
| CN106267201A (en) * | 2016-08-26 | 2017-01-04 | 深圳先进技术研究院 | A kind of black phosphorus of polymer wrapped and preparation method and application |
| CN109913201A (en) * | 2019-04-01 | 2019-06-21 | 苏州大学 | Two area's fluorescent nano probe of near-infrared and its preparation and application based on black phosphorus |
| CN110950313A (en) * | 2019-12-25 | 2020-04-03 | 深圳市中科墨磷科技有限公司 | Method for preparing polycrystalline black phosphorus nanosheets by hydrothermal etching method |
-
2022
- 2022-06-23 CN CN202210719337.2A patent/CN115108539A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
| CN106267201A (en) * | 2016-08-26 | 2017-01-04 | 深圳先进技术研究院 | A kind of black phosphorus of polymer wrapped and preparation method and application |
| CN109913201A (en) * | 2019-04-01 | 2019-06-21 | 苏州大学 | Two area's fluorescent nano probe of near-infrared and its preparation and application based on black phosphorus |
| CN110950313A (en) * | 2019-12-25 | 2020-04-03 | 深圳市中科墨磷科技有限公司 | Method for preparing polycrystalline black phosphorus nanosheets by hydrothermal etching method |
Non-Patent Citations (3)
| Title |
|---|
| LI ZENG等: "Surface and interface control of black phosphorus", 《CHEM》, vol. 8 * |
| RIJUN GUI等: "Black phosphorus quantum dots: synthesis, properties, functionalized modification and applications", 《CHEM SOC REV》, vol. 47 * |
| 刘程主编: "《表面活性剂性质理论与应用》", 30 June 2003, 北京工业大学出版社, pages: 101 * |
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