CN110627029A - Black phosphorus quantum dot/nanosheet composite material and preparation method thereof - Google Patents
Black phosphorus quantum dot/nanosheet composite material and preparation method thereof Download PDFInfo
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- CN110627029A CN110627029A CN201911037880.9A CN201911037880A CN110627029A CN 110627029 A CN110627029 A CN 110627029A CN 201911037880 A CN201911037880 A CN 201911037880A CN 110627029 A CN110627029 A CN 110627029A
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- 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
Abstract
The invention discloses a black phosphorus quantum dot/nanosheet composite material and a preparation method thereof, belonging to the technical field of composite material preparation and comprising the following steps: s1: preparing a black phosphorus dispersion liquid; s2: respectively carrying out first-step microwave treatment and second-step microwave treatment on the S1 black phosphorus dispersion liquid to prepare a mixture; s3: centrifuging the S2 mixture to obtain a black phosphorus nanosheet dispersion liquid; s4: carrying out microwave treatment on the S3 black phosphorus nanosheet dispersion liquid to prepare a black phosphorus quantum dot/nanosheet composite material; compared with ultrasonic treatment, the method has very short treatment time, and does not need any surfactant or ultrasound to obtain stable few-layer black phosphorus; when microwave irradiation acts on a sample, Van der Waals interaction between the black phosphorus bulk thin slices begins to weaken, and the black phosphorus bulk thin slices are peeled off layer by layer in a proper solvent, so that the structure that the black phosphorus quantum dots grow on the slices is effectively realized.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a black phosphorus quantum dot/nanosheet composite material and a preparation method thereof.
Background
Black Phosphorus (BP), which is very graphite-like in appearance, performance and structure, appears black, flaky, and is electrically conductive, with the linking atoms appearing as wrinkled sheets. Phonons, photons and electronic electrons in the layered black phosphorus structure show high anisotropy, and have great potential application value in electronic thin film and infrared photoelectronic technology. Light absorption in black phosphor is very sensitive to light polarization, film thickness and doping. Black phosphorus phototransistors also exhibit hyperspectral detection in infrared and visible light. Black phosphorus also includes the possibility of exfoliation, forming phosphenes, a graphite-like material with excellent electron transfer properties, similar to graphite.
The method for obtaining high-quality two-dimensional black phosphorus is the most critical preparation link, the research idea is similar to the preparation of graphene with a similar structure, the main research is concentrated in nearly two years, so the preparation of the two-dimensional black phosphorus is still in the preliminary stage of research, and the industrialization needs a current day. The current methods for preparing two-dimensional black phosphorus mainly comprise three methods: mechanical lift-off, liquid phase lift-off, pulsed laser deposition.
In the liquid phase stripping method, ultrasonic treatment is the most commonly used, but the ultrasonic treatment needs a longer time, the transverse dimension can be reduced along with the lengthening of the ultrasonic time, and abnormal structural defects are caused in the two-dimensional nano-sheet, and the two-dimensional nano-sheet obtained by the method, and the composite material of the black phosphorus quantum dot and the nano-sheet is not reported.
Disclosure of Invention
The invention aims to provide a black phosphorus quantum dot/nanosheet composite material and a preparation method thereof, aiming at the defects in the prior art.
The first purpose of the invention is to provide a preparation method of a black phosphorus quantum dot/nanosheet composite material, which comprises the following steps:
s1: preparing a black phosphorus dispersion liquid;
s2: respectively carrying out first-step microwave treatment and second-step microwave treatment on the S1 black phosphorus dispersion liquid to prepare a mixture;
the microwave treatment conditions of the first step are as follows: the microwave temperature is 45-55 ℃, the microwave power is 550-650W, and the time is 15-25 min; the second microwave treatment condition is as follows: the microwave temperature is 65-75 ℃, the microwave power is 180-220W, and the time is 2-5 min;
s3: centrifuging the S2 mixture, and taking the upper layer liquid to obtain a black phosphorus nanosheet dispersion liquid;
s4: and (3) carrying out microwave treatment on the S3 black phosphorus nanosheet dispersion liquid for 5-15 min at the temperature of 115-125 ℃ and the microwave power of 550-650W to obtain the black phosphorus quantum dot/nanosheet composite material.
Preferably, the black phosphorus dispersion liquid in S1 is prepared by the following steps:
putting black phosphorus in a saturated NaOH/NMP (N-methyl pyrrolidone) solution, and uniformly stirring to prepare a black phosphorus dispersion liquid; black phosphorus: the dosage ratio of NaOH to NMP is 4-6 mg: 1 ml.
Preferably, the centrifugation treatment in S3 is carried out at a centrifugation speed of 5500-6500 rpm for 15-25 min, and then the centrifugation is continued at 8500-9500 rpm for 15-25 min.
The second purpose of the invention is to provide the black phosphorus quantum dot/nanosheet composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts a two-step microwave method, firstly uses high-power microwave to treat blocky black phosphorus dispersion liquid to destroy van der Waals force between black phosphorus layers, then uses low-power microwave to treat the blocky black phosphorus to further separate the blocky black phosphorus into few layers of black phosphorus sheets, and obtains the black phosphorus nano sheets with required size through centrifugal treatment and separation; the centrifuged black phosphorus nanosheets are subjected to one-step microwave treatment, so that the fragmentation effect of the nanosheets is effectively realized, and the compounding of the nanosheets and the quantum dots is realized; compared with ultrasonic treatment, the method has very short treatment time, and does not need any surfactant or ultrasound to obtain stable and few-layer black phosphorus; when microwave irradiation acts on a sample, Van der Waals interaction between the black phosphorus bulk thin slices begins to weaken, and the black phosphorus bulk thin slices are peeled off layer by layer in a proper solvent, so that the structure that the black phosphorus quantum dots grow on the slices is effectively realized.
Drawings
FIG. 1 is a transmission diagram of a black phosphorus quantum dot/nanosheet composite prepared in example 1;
FIG. 2 is an electron diffraction pattern of the region shown in FIG. 1;
fig. 3 is a transmission diagram of a local area of the black phosphorus quantum dot/nanosheet composite prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
A preparation method of a black phosphorus quantum dot/nanosheet composite material comprises the following steps:
(1) preparing a saturated NaOH/NMP solution (the NaOH and the NMP can be mixed at any ratio until the mixture is saturated);
(2) weighing block black phosphorus, and preparing 5mg/ml BP-saturated NaOH/NMP dispersion liquid;
(3) treating the BP-saturated NaOH/NMP dispersion liquid in the step (2) for 20min under the conditions that the microwave temperature is 50 ℃ and the microwave power is 600W; then processing for 3min under the conditions that the microwave temperature is 70 ℃ and the microwave power is 200W to prepare a mixture;
(4) centrifuging the mixture obtained in the step (3), wherein the centrifugal speed is set to be 6000rpm/min, and the time is set to be 20 min; continuing to centrifuge, setting the centrifugal speed at 9000rpm/min for 20min, and taking the upper layer liquid to obtain a black phosphorus nanosheet dispersion liquid;
(5) and (4) treating the black phosphorus nanosheet dispersion liquid prepared in the step (4) for 10min under the conditions that the microwave temperature is 120 ℃ and the microwave power is 600W to prepare the black phosphorus quantum dot/nanosheet composite material.
Example 2
A preparation method of a black phosphorus quantum dot/nanosheet composite material comprises the following steps:
(1) preparing a saturated NaOH/NMP solution (the NaOH and the NMP can be mixed at any ratio until the mixture is saturated);
(2) weighing block black phosphorus, and preparing 4mg/ml BP-saturated NaOH/NMP dispersion liquid;
(3) treating the BP-saturated NaOH/NMP dispersion liquid in the step (2) for 15min under the conditions that the microwave temperature is 45 ℃ and the microwave power is 550W; then processing for 2min under the conditions that the microwave temperature is 65 ℃ and the microwave power is 180W to prepare a mixture;
(4) centrifuging the mixture obtained in the step (3), setting the centrifugal rotation speed to be 6500rpm/min and the time to be 15min, continuing centrifuging, setting the centrifugal rotation speed to be 8500rpm/min and the time to be 15min, and taking the upper-layer liquid to obtain a black phosphorus nanosheet dispersion liquid;
(5) and (4) treating the black phosphorus nanosheet dispersion liquid prepared in the step (4) for 5min at the microwave temperature of 115 ℃ and the microwave power of 650W to prepare the black phosphorus quantum dot/nanosheet composite material.
Example 3
A preparation method of a black phosphorus quantum dot/nanosheet composite material comprises the following steps:
(1) preparing a saturated NaOH/NMP solution (the NaOH and the NMP can be mixed at any ratio until the mixture is saturated);
(2) weighing block black phosphorus, and preparing 6mg/ml BP-saturated NaOH/NMP dispersion liquid;
(3) treating the BP-saturated NaOH/NMP dispersion liquid in the step (2) for 25min at the microwave temperature of 55 ℃ and the microwave power of 650W; then processing for 5min under the conditions that the microwave temperature is 75 ℃ and the microwave power is 220W to prepare a mixture;
(4) centrifuging the mixture obtained in the step (3), setting the centrifugal rotation speed to be 5500rpm/min and the time to be 25min, continuing centrifuging, setting the centrifugal rotation speed to be 9500rpm/min and the time to be 25min, and taking the upper-layer liquid to obtain a black phosphorus nanosheet dispersion liquid;
(5) and (4) treating the black phosphorus nanosheet dispersion liquid prepared in the step (4) for 15min under the conditions that the microwave temperature is 125 ℃ and the microwave power is 550W to prepare the black phosphorus quantum dot/nanosheet composite material.
The performances of the black phosphorus quantum dot/nanosheet composite materials prepared in the above examples 1-3 are similar, and the effects of the method of the present invention will be described below by taking the black phosphorus quantum dot/nanosheet composite material prepared in example 1 as an example only.
FIG. 1 is a transmission diagram of a black phosphorus quantum dot/nanosheet composite, which can be obtained from FIG. 1, wherein the black phosphorus quantum dot appears on a large-sized black phosphorus nanosheet, thereby illustrating that the black phosphorus nanosheet/quantum dot composite can be successfully prepared by using the method of the present invention; FIG. 2 is an electron diffraction pattern of the region shown in FIG. 1, which is obtained from FIG. 2, and which demonstrates that the composite material of black phosphorus nanosheets/quantum dots is polycrystalline; from fig. 3, it can be seen that the transmission diagram of the composite situation of a whole complete black phosphorus nanosheet and black phosphorus quantum dots shows that the size of the black phosphorus nanosheet is about 1 μm × 1 μm, the black phosphorus quantum dots are more uniformly compounded on the black phosphorus nanosheet, and our conclusion can be verified.
In summary, the invention adopts a two-step microwave method, firstly, high-power microwave is used to treat the block-shaped black phosphorus dispersion liquid to destroy van der waals force between black phosphorus layers, then low-power microwave treatment is used to further separate the block-shaped black phosphorus into a few layers of black phosphorus sheets, and the black phosphorus nanosheets with the required size are obtained through centrifugal treatment and separation; the centrifuged black phosphorus nanosheets are subjected to one-step microwave treatment, so that the fragmentation effect of the nanosheets is effectively realized, the compounding of the nanosheets and the quantum dots is realized, and compared with ultrasonic treatment, the method has the advantages that the treatment time is very short, and no surfactant or ultrasonic is needed to obtain stable few-layer black phosphorus; when microwave irradiation acts on a sample, Van der Waals interaction between the black phosphorus bulk thin slices begins to weaken, and the black phosphorus bulk thin slices are peeled off layer by layer in a proper solvent, so that the structure that the black phosphorus quantum dots grow on the slices is effectively realized.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (4)
1. A preparation method of a black phosphorus quantum dot/nanosheet composite material is characterized by comprising the following steps:
s1: preparing a black phosphorus dispersion liquid;
s2: respectively carrying out first-step microwave treatment and second-step microwave treatment on the S1 black phosphorus dispersion liquid to prepare a mixture;
the microwave treatment conditions of the first step are as follows: the microwave temperature is 45-55 ℃, the microwave power is 550-650W, and the time is 15-25 min; the second microwave treatment condition is as follows: the microwave temperature is 65-75 ℃, the microwave power is 180-220W, and the time is 2-5 min;
s3: centrifuging the S2 mixture, and taking the upper layer liquid to obtain a black phosphorus nanosheet dispersion liquid;
s4: and (3) carrying out microwave treatment on the S3 black phosphorus nanosheet dispersion liquid for 5-15 min at the temperature of 115-125 ℃ and the microwave power of 550-650W to obtain the black phosphorus quantum dot/nanosheet composite material.
2. The preparation method of the black phosphorus quantum dot/nanosheet composite material as claimed in claim 1, wherein the black phosphorus dispersion in S1 is specifically prepared by:
putting black phosphorus in a saturated NaOH/NMP solution, and uniformly stirring to prepare a black phosphorus dispersion liquid; black phosphorus: the dosage ratio of NaOH to NMP is 4-6 mg: 1 ml.
3. The preparation method of the black phosphorus quantum dot/nanosheet composite material according to claim 1, wherein the centrifuging condition in S3 is that the centrifuging speed is 5500-6500 rpm/min for 15-25 min, and then centrifuging is continued, and the centrifuging speed is 8500-9500 rpm/min for 15-25 min.
4. The black phosphorus quantum dot/nanosheet composite material prepared by the preparation method according to any one of claims 1 to 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517295A (en) * | 2020-06-02 | 2020-08-11 | 陕西科技大学 | Two-dimensional mesh black phosphorus material and controllable and adjustable preparation method thereof |
| CN113336205A (en) * | 2021-07-15 | 2021-09-03 | 西安地球环境创新研究院 | Preparation method and application of black phosphorus quantum dot with up-conversion effect |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106190120A (en) * | 2016-06-30 | 2016-12-07 | 深圳先进技术研究院 | A kind of black phosphorus quantum dot and preparation method thereof |
| CN106892426A (en) * | 2017-03-24 | 2017-06-27 | 福州大学 | The preparation method of Graphene and black phosphorus quantum dot composite material |
| 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 |
| CN108033443A (en) * | 2017-12-14 | 2018-05-15 | 华南理工大学 | A kind of method that combination of ultrasound microwave prepares graphene quantum dot |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN109628994A (en) * | 2019-01-12 | 2019-04-16 | 河南大学 | A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation |
-
2019
- 2019-10-29 CN CN201911037880.9A patent/CN110627029A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106190120A (en) * | 2016-06-30 | 2016-12-07 | 深圳先进技术研究院 | A kind of black phosphorus quantum dot and preparation method thereof |
| CN106892426A (en) * | 2017-03-24 | 2017-06-27 | 福州大学 | The preparation method of Graphene and black phosphorus quantum dot composite material |
| 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 |
| CN108033443A (en) * | 2017-12-14 | 2018-05-15 | 华南理工大学 | A kind of method that combination of ultrasound microwave prepares graphene quantum dot |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN109628994A (en) * | 2019-01-12 | 2019-04-16 | 河南大学 | A kind of preparation method of orthogonal black phosphorus crystal and black phosphorus quantum dot using orthogonal black phosphorus crystal preparation |
Non-Patent Citations (4)
| Title |
|---|
| CHONGYANG ZHU: "Ultrafast Preparation of Black Phosphorus Quantum Dots for Efficient Humidity Sensing", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| MUNKHBAYAR BATMUNKH: "Microwave-assisted synthesis of black phosphorus quantum dots: efficient electrocatalyst for oxygen evolution reaction", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| MUNKHJARGAL BAT-ERDENE: "Efficient and Fast Synthesis of Few-Layer Black Phosphorus via Microwave-Assisted Liquid-Phase Exfoliation", 《SMALL METHODS》 * |
| 侯振江，等: "《生物化学检验技术》", 31 August 2014 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517295A (en) * | 2020-06-02 | 2020-08-11 | 陕西科技大学 | Two-dimensional mesh black phosphorus material and controllable and adjustable preparation method thereof |
| CN113336205A (en) * | 2021-07-15 | 2021-09-03 | 西安地球环境创新研究院 | Preparation method and application of black phosphorus quantum dot with up-conversion effect |
| CN113336205B (en) * | 2021-07-15 | 2023-12-12 | 西安地球环境创新研究院 | Preparation method and application of black phosphorus quantum dot with up-conversion effect |
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