CN113213441A - Preparation method of alcoholized black phosphorus stably dissolved in aqueous solution - Google Patents
Preparation method of alcoholized black phosphorus stably dissolved in aqueous solution Download PDFInfo
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- CN113213441A CN113213441A CN202110517889.0A CN202110517889A CN113213441A CN 113213441 A CN113213441 A CN 113213441A CN 202110517889 A CN202110517889 A CN 202110517889A CN 113213441 A CN113213441 A CN 113213441A
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- black phosphorus
- aqueous solution
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- polyethylene glycol
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
Abstract
The invention belongs to the technical field of functional materials, and relates to a preparation method of pegylated black phosphorus with high luminous performance in an aqueous solution, which can stably exist in the aqueous solution, and avoids the defect that the black phosphorus easily reacts with water molecules and oxygen in the water. The method for preparing the alcoholized black phosphorus stably dissolved in the aqueous solution completely isolates the black phosphorus from oxygen and water by forming a layer of uniform polyethylene glycol on the surface of the black phosphorus, and has stronger luminous performance in a visible light range; compared with pure black phosphorus, the black phosphorus modified by polyethylene glycol provided by the invention has better optical performance.
Description
Technical Field
The invention belongs to the technical field of preparation of two-dimensional nano materials, and particularly relates to a preparation method of alcoholized black phosphorus stably dissolved in an aqueous solution.
Background
As a novel two-dimensional material, the Black Phosphorus (BP) has a lamellar structure similar to graphene, a fold structure and an adjustable direct band gap, so that the black phosphorus has unique in-plane anisotropy and excellent physical properties, researches show that the black phosphorus has an ultra-high specific surface area and good biocompatibility, is widely used as a drug sustained-release carrier and a diagnosis and treatment integrated material (Advanced materials.2017,29 and 1) for cancer in the field of biomedicine, has high photo-thermal conversion efficiency, and shows great application value in the field of photoelectricity.
Compared with white phosphorus and red phosphorus allotropes, the black phosphorus has the weakest reactivity, and researches show that compared with other two-dimensional materials such as graphene, graphene oxide, molybdenum disulfide and the like, the black phosphorus has poor stability in a physiological environment, is easy to react with oxygen and water to generate phosphoric acid, and causes structural damage, so that the physicochemical properties such as photo-thermal property and the like of the black phosphorus are influenced, and the stability of the black phosphorus becomes a key problem for restricting the development of black phosphorus materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of black phosphorus alcoholate stably dissolved in aqueous solution, which is characterized in that a layer of uniform polyethylene glycol is formed on the surface of black phosphorus to completely isolate the black phosphorus from oxygen and water, and the black phosphorus alcoholate prepared by the method is dissolved in alcohol and aqueous solution, has stronger luminous performance in the visible light range and has great potential application value in the aspect of photoelectronic devices through characterization; meanwhile, the polyethylene glycol has super-strong viscosity and good biocompatibility, so that the prepared polyethylene glycol modified black phosphorus is expected to be applied to the field of biomedicine, and compared with pure black phosphorus, the polyethylene glycol modified black phosphorus provided by the invention has better optical performance.
The invention has simple production process and high yield, uses water as the solvent, is environment-friendly and can realize low-cost large-scale production. The material is modified, and polyethylene glycol is introduced to the surface of black phosphorus by using an organic solvent, so that the stability of the black phosphorus in the air is improved.
The invention provides a preparation method of alcoholized black phosphorus stably dissolved in an aqueous solution, which comprises the following three steps:
firstly, weighing red phosphorus and agate beads, mixing and placing the red phosphorus and the agate beads in a sealing tank, sealing the sealing tank under the protection of argon, and keeping the weight of opposite angles of planetary ball milling consistent;
secondly, keeping the set rotating speed for ball milling, opening a tank in a glove box in the middle, adding polyethylene glycol, and keeping the previous rotating speed for ball milling under protective gas;
and thirdly, dispersing a proper amount of the sample after the ball milling in a solvent, performing water bath ultrasound, and centrifuging to obtain the lower-layer pegylated black phosphorus.
Preferably, the mass ratio of the red phosphorus to the agate in the first step is 1: 100, and the agate has 3 different sizes, and the ratio is 1: 1.
In any of the above schemes, preferably, in the second step, the rotation speed of the ball mill reaches 1400r/min, polyethylene glycol is added after ball milling is carried out for 72 hours, the ratio of the polyethylene glycol to red phosphorus is 4: 1, and ball milling is continued for 96 hours under the protection of argon.
In any of the above schemes, preferably, the ultrasonic time of the water bath in the third step is 5-15min, the power is 200W, the temperature of the water bath is 0-10 ℃, the centrifugal speed is 11000r/min, and the centrifugal time is 15-20 min.
In any of the above embodiments, preferably, the solvent in which the sample is dispersed in the third step is water or alcohol.
In any of the above embodiments, preferably, the polyethylene glycol is in the form of particles having a molecular weight of 4000.
In any of the above schemes, preferably, the centrifuged lower layer precipitate shows (021) crystal orientation black phosphorus, and the pegylated black phosphorus shows greatly improved stability through XRD and raman spectroscopy analysis.
The invention provides black phosphorus modified by polyethylene glycol, which is prepared by forming a layer of uniform polyethylene glycol on the surface of black phosphorus,
the invention has the following advantages:
1. the alcoholized black phosphorus is successfully prepared, and the obtained alcoholized black phosphorus has higher crystallinity through XRD and Raman spectrograms;
2. the alcoholized black phosphorus obtained by the preparation process and the method has higher luminous performance in a visible light range, and can be used in the corresponding photoelectric field;
3. the solvent used in the process of synthesizing the black phosphorus modified by the polyethylene glycol is water, the solvent is nontoxic, the used raw material polyethylene glycol has super-strong viscosity and good biocompatibility, and the black phosphorus modified by the polyethylene glycol is of a spherical nano structure;
4. the black phosphorus modified by the polyethylene glycol has stronger luminous performance through an absorption spectrogram and a photoluminescence spectrum, and has better application prospect in photoelectric components.
Drawings
FIG. 1 is a Raman spectrum of polyethylene glycol modified black phosphorus.
Figure 2 is an XRD pattern of polyethylene glycol modified black phosphorus.
FIG. 3 is a diagram of the ultraviolet absorption spectrum of black phosphorus modified by polyethylene glycol.
FIG. 4 shows the photoluminescence spectrum of a polyethylene glycol-modified black phosphorus.
Detailed Description
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. The following description will further describe the specific embodiment of the method for preparing the black phosphorus alcoholate stably dissolved in the aqueous solution according to the present invention with reference to the attached drawings.
As shown in fig. 1-4, the preparation method of the alcoholized black phosphorus stably dissolved in the aqueous solution is shown in the process diagram.
Example 1:
the invention provides a preparation method of alcoholized black phosphorus stably dissolved in an aqueous solution, which comprises the following steps:
(1) weighing 3.00g of red phosphorus powder and 300g of three agate beads with different sizes, and placing the red phosphorus powder and the agate beads in a sealed tank protected by argon; the rotating speed of the ball mill is required to be maintained at 1400r/min, ball milling is carried out for 72 hours, and then red phosphorus: polyethylene glycol 1: 4, adding polyethylene glycol, adding 12g of polyethylene glycol under the protection of argon, and continuing ball milling for 96 hours under the same experimental conditions; taking a proper amount of sample, adding 40ml of ultrapure water, carrying out ultrasonic treatment for 10min under the protection of argon, centrifuging the solution at 11000rpm for 20min, and taking a precipitate to finally obtain the pegylated black phosphorus (PEG BP).
(2) Dissolving the black phosphorus modified by polyethylene glycol in an alcohol spray film, representing a Raman spectrogram, an ultraviolet absorption spectrum, PL and XRD of the black phosphorus, finding that the black phosphorus obtained by ball milling and adding the polyethylene glycol has a crystal form of (021), has higher crystallinity, improves the stability of the black phosphorus, and the polyethylene glycol on the surface has a certain isolation effect on oxygen and water.
Example 2:
the invention provides a preparation method of alcoholized black phosphorus stably dissolved in an aqueous solution, which comprises the following steps:
in the example, the crystal form of the black phosphorus obtained by ball milling is (021) by dissolving the black phosphorus in an alcohol solvent, the crystallinity is higher, and the stability of the black phosphorus is improved.
The other steps were the same as in example 1.
Example 3:
the invention provides a preparation method of alcoholized black phosphorus stably dissolved in an aqueous solution, which comprises the following steps:
the black phosphorus modified by polyethylene glycol is dissolved in a small amount of alcohol for spin coating to form a film, the Raman spectrogram, the ultraviolet absorption spectrum, the PL and the XRD are represented, the black phosphorus is obtained by pegylation, the stability of the black phosphorus is improved, and the polyethylene glycol on the surface plays a certain role in isolating oxygen and water.
The other steps were the same as in example 1.
Claims (6)
1. A preparation method of alcoholized black phosphorus stably dissolved in aqueous solution is characterized in that: the preparation method comprises the following three steps:
firstly, weighing red phosphorus and agate beads, mixing and placing the red phosphorus and the agate beads in a sealing tank, sealing the sealing tank under the protection of argon, and keeping the weight of opposite angles of planetary ball milling consistent;
secondly, keeping the set rotating speed for ball milling, opening a tank in a glove box in the middle, adding polyethylene glycol, and keeping the previous rotating speed for ball milling under protective gas;
and thirdly, dispersing a proper amount of the sample after the ball milling in a solvent, performing water bath ultrasound, and centrifuging to obtain the lower-layer pegylated black phosphorus.
2. The process for the preparation of alcoholized black phosphorus stably dissolved in aqueous solution according to claim 1, characterized in that: in the first step, the mass ratio of red phosphorus to agate is 1: 100, and the agate has 3 different sizes, and the ratio is 1: 1.
3. The process for the preparation of alcoholized black phosphorus stably dissolved in aqueous solution according to claim 1, characterized in that: and in the second step, the rotating speed of the ball mill reaches 1400r/min, polyethylene glycol is added after ball milling is carried out for 72 hours, the ratio of the polyethylene glycol to red phosphorus is 4: 1, and ball milling is continued for 96 hours under the protection of argon.
4. The process for the preparation of alcoholized black phosphorus stably dissolved in aqueous solution according to claim 1, characterized in that: and in the third step, the ultrasonic time of the water bath is 5-15min, the power is 200W, the temperature of the water bath is 0-10 ℃, the centrifugal speed is 11000r/min, and the centrifugal time is 15-20 min.
5. The process for the preparation of alcoholized black phosphorus stably dissolved in aqueous solution, as claimed in claim 1 or 4, wherein: the solvent for dispersing the sample in the third step is water and alcohol.
6. The process for the preparation of alcoholized black phosphorus stably dissolved in aqueous solution according to claim 1, characterized in that: the polyethylene glycol is granular and has the molecular weight of 4000.
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Citations (5)
| 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 |
| CN107628592A (en) * | 2017-09-29 | 2018-01-26 | 福州大学 | A kind of black phosphorus quantum dot of PEG modifications and its preparation method and application |
| CN110040703A (en) * | 2019-04-23 | 2019-07-23 | 清华大学 | A kind of preparation method and application of hydroxylating black phosphorus quantum dot group water solution |
| CN110092361A (en) * | 2019-04-23 | 2019-08-06 | 清华大学 | A kind of preparation method and application of the black phosphorus material of hydroxyl modified |
| US20200189914A1 (en) * | 2018-12-13 | 2020-06-18 | Lockheed Martin Corporation | Modified track-etched substrates for composite graphene membranes |
-
2021
- 2021-05-12 CN CN202110517889.0A patent/CN113213441A/en active Pending
Patent Citations (5)
| 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 |
| CN107628592A (en) * | 2017-09-29 | 2018-01-26 | 福州大学 | A kind of black phosphorus quantum dot of PEG modifications and its preparation method and application |
| US20200189914A1 (en) * | 2018-12-13 | 2020-06-18 | Lockheed Martin Corporation | Modified track-etched substrates for composite graphene membranes |
| CN110040703A (en) * | 2019-04-23 | 2019-07-23 | 清华大学 | A kind of preparation method and application of hydroxylating black phosphorus quantum dot group water solution |
| CN110092361A (en) * | 2019-04-23 | 2019-08-06 | 清华大学 | A kind of preparation method and application of the black phosphorus material of hydroxyl modified |
Non-Patent Citations (2)
| Title |
|---|
| 勃劳尔等: "《无机制备化学手册（增订第二版） 上册》", 28 February 1975, 燃料化学工业出版社 * |
| 李成印等: "磷烯的制备、性质及应用研究进展", 《深圳大学学报（理工版）》 * |
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Inventor after: Peng Maiju Inventor after: Chen Jiarong Inventor after: Ren Dasen Inventor before: Peng Maiju |
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Application publication date: 20210806 |