CN111807339B - Water-based preparation method of black phosphorus quantum dots - Google Patents
Water-based preparation method of black phosphorus quantum dots Download PDFInfo
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- CN111807339B CN111807339B CN202010725880.4A CN202010725880A CN111807339B CN 111807339 B CN111807339 B CN 111807339B CN 202010725880 A CN202010725880 A CN 202010725880A CN 111807339 B CN111807339 B CN 111807339B
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Abstract
The invention discloses a water-based preparation method of black phosphorus quantum dots, which comprises the following steps: mixing red phosphorus and deionized water, and carrying out hydrothermal treatment at the temperature of 200-220 ℃ for 24-72 hours to obtain the black phosphorus quantum dot aqueous solution. The method only takes the aqueous solution as the solvent, and prepares the black phosphorus quantum dot by hydrothermal reaction with the red phosphorus, so that the problem that a large amount of toxic and explosive organic solvent is used in the traditional preparation process of the black phosphorus quantum dot is solved, and the prepared black phosphorus quantum dot has the advantages of no toxicity and environmental friendliness.
Description
Technical Field
The invention belongs to the field of low-dimensional semiconductor materials, and particularly relates to a water-based preparation method of black phosphorus quantum dots.
Background
Black Phosphorus (BP) is widely used in the development of nano-optoelectronic materials and devices due to its high carrier mobility, adjustable direct band gap, and unique in-plane anisotropy. The quantum dots not only have the excellent characteristics of black phosphorus, but also show the size effect, the confinement effect, the tunneling effect and the surface effect of the quantum dots, have unique advantages in photoelectric properties compared with other materials, and are widely applied to the research and development of photoelectric devices in the fields of chemical sensing, environmental remediation, biological marking and the like.
At present, some preparation technologies of black phosphorus quantum dots exist. By high-pressure conversion of white phosphorus or by Red Phosphorus (RP) and Sn, SnI4The block black phosphorus can be obtained by co-firing preparation, and on the basis, the block black phosphorus can be stripped by using a mechanical stripping method to form the black phosphorus two-dimensional material, but the obtained material has larger size. Or a liquid phase stripping method is used, so that the Black Phosphorus Quantum Dots (BPQD) with complete crystal structures, no defects and controllable one-dimensional sizes can be obtained. However, this process requiresA large amount of toxic and explosive organic solvents are used, and if the method is applied to actual production, not only great cost is required to be invested in the aspects of ecological environment protection and personnel safety protection, but also potential safety hazards are brought to each link of storage, transfer, production and the like. Therefore, a simple, cheap and environment-friendly preparation method of the black phosphorus nano material needs to be found.
Disclosure of Invention
Aiming at the problems, the invention researches and designs a water-based preparation method of the black phosphorus quantum dot to solve the defects that the black phosphorus quantum dot prepared by the traditional method is large in size, uses a toxic and explosive organic solvent in the preparation process and has potential safety hazard. The technical means adopted by the invention are as follows:
a water-based preparation method of black phosphorus quantum dots comprises the following steps: mixing red phosphorus and deionized water, and carrying out hydrothermal treatment at the temperature of 200-220 ℃ for 24-72 hours to obtain the black phosphorus quantum dot aqueous solution.
Preferably, the mass ratio of red phosphorus to deionized water is 1: (32-1800).
Preferably, the treatment temperature is 200-.
Preferably, the treatment time is 48-72 hours.
Preferably, the fineness of the red phosphorus is 80-300 mesh.
Compared with the prior art, the water-based preparation method of the black phosphorus quantum dot has the following beneficial effects: the method only takes the aqueous solution as the solvent, and prepares the black phosphorus quantum dot by hydrothermal reaction with the red phosphorus, so that the problem that a large amount of toxic and explosive organic solvent is used in the traditional preparation process of the black phosphorus quantum dot is solved, and the prepared black phosphorus quantum dot has the advantages of no toxicity and environmental friendliness.
Drawings
FIG. 1 is a schematic diagram of (a) HRTEM morphology graph, (b) high resolution lattice diffraction graph and (c) corresponding black phosphorus structure of black phosphorus quantum dots prepared by water-based method in the embodiment of the invention.
FIG. 2 is a graph of fluorescence emission spectra of black phosphorus quantum dots prepared in the examples of the present invention and their relationship with aqueous solution concentration.
FIG. 3 shows an X-ray diffraction pattern of red phosphorus and an X-ray diffraction pattern of a dried black phosphorus quantum dot solution in an embodiment of the present invention.
Detailed Description
The synthesis method of the black phosphorus quantum dot comprises the following steps:
(1) selecting a point X in the range of 0.01g-0.5g of the usage amount of red phosphorus at intervals of not less than 0.001 from small to large;
(2) selecting a point Y in the deionized water usage amount of 16ml-18ml from small to large at intervals of not less than 0.1;
(3) selecting a point T from a small interval to a large interval of 5 within the temperature range of 200-220 ℃;
(4) selecting a point H from 12 in the reaction time range of 24-72 hours from small to large;
(5) weighing Xg red phosphorus, mixing the red phosphorus with Yml deionized water, putting the mixture into a hydrothermal kettle with the capacity of 20ml, and placing the hydrothermal kettle in a constant temperature box for hydrothermal reaction for H hours at T degree to obtain a clear and transparent black phosphorus quantum dot aqueous solution;
(6) different condition parameters are selected: combining the precursor particle size (80 meshes, 200 meshes and 300 meshes, the larger the mesh, the finer the particle size), the solute-solvent ratio (between 1:32 and 1:1800), the hydrothermal reaction temperature (200, 205, 210, 215 and 220 ℃), the time (24, 36, 48, 60 and 72 hours), and repeating the steps (1) to (5) to obtain a plurality of groups of black phosphorus quantum dot aqueous solutions;
(7) the obtained black phosphorus quantum dot aqueous solution with different condition parameters is measured by a fluorescence spectrophotometer, and the black phosphorus conversion effect under different parameter conditions can be seen.
FIG. 1 is a schematic diagram of (a) HRTEM morphology graph, (b) high resolution lattice diffraction graph and (c) corresponding black phosphorus structure of black phosphorus quantum dots prepared by water-based method in the embodiment of the invention. As shown in FIG. 1, HRTEM analysis shows that the average size of the prepared black phosphorus quantum dots is about 3.7nm, the typical interplanar spacing is 0.203nm, and the theoretical value is very close to 0.207 nm.
FIG. 2 is a graph of fluorescence emission spectra of black phosphorus quantum dots prepared in the examples of the present invention and their relationship with aqueous solution concentration. The different prepared black phosphorus quantum dot solutions were analyzed by PL, and as shown in fig. 2, the greater the difference in height between the small peak on the left (red phosphorus peak) and the large peak on the right (black phosphorus peak) in the graph, the higher the conversion rate of red phosphorus. The steps corresponding to the curves in the figure are as follows: 0.005g, 0.01g, 0.02g, 0.05g, 0.06g or 0.084g of RP having a particle size of 80 mesh was mixed with deionized water having a volume of 16.2ml, and reacted in a 200 ℃ incubator for 48 hours. The comparison shows that when the usage amount of the red phosphorus is about 0.02g, the obtained black phosphorus quantum dot solution has the highest concentration, namely the black phosphorus conversion effect is the best.
FIG. 3 shows an X-ray diffraction pattern of red phosphorus and an X-ray diffraction pattern of a dried black phosphorus quantum dot solution in an embodiment of the present invention. As can be seen from fig. 3, XRD shows diffraction peaks of crystals, which are different from crystal to crystal, thus demonstrating that the substance is changed. XRD analysis is carried out on the original red phosphorus crystal and the crystal obtained after the prepared solution is dried, the difference of diffraction peaks of the original red phosphorus crystal and the crystal obtained after the prepared solution is dried is found, and a new substance generated in the newly prepared solution can be inferred, namely the black phosphorus quantum dot is prepared by the method provided by the invention.
The invention uses red phosphorus as raw material, uses a black phosphorus quantum dot water-based preparation method from bottom to top, summarizes the growth process rule of the crystal in the aqueous solution by changing the condition parameters of red phosphorus particle size (80 meshes, 200 meshes and 300 meshes, the larger the mesh is, the finer the particle size is), solute-solvent ratio (1:32 to 1:1800), hydrothermal reaction temperature (200, 205, 210, 215 and 220 ℃), time (24, 36, 48, 60 and 72 hours) and the like, and obtains the environment-friendly preparation method with higher black phosphorus quantum dot yield (high fluorescence spectrum curve peak value) by curve analysis summary obtained by measuring the fluorescence spectrum by a fluorescence spectrophotometer.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (3)
1. A water-based preparation method of black phosphorus quantum dots is characterized by comprising the following steps: the method comprises the following steps: mixing red phosphorus and deionized water, and carrying out hydrothermal treatment at the temperature of 200-220 ℃, wherein the fineness of the red phosphorus is 80-300 meshes, the mass ratio of the red phosphorus to the deionized water is 1: 32-1800, and the treatment time is 24-72 hours, so as to obtain the black phosphorus quantum dot aqueous solution.
2. The water-based preparation method of the black phosphorus quantum dot according to claim 1, wherein the water-based preparation method comprises the following steps: the treatment temperature is 200-210 ℃.
3. The water-based preparation method of the black phosphorus quantum dot according to claim 1, wherein the water-based preparation method comprises the following steps: the treatment time is 48-72 hours.
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| CN105948004B (en) * | 2016-05-06 | 2021-05-07 | 吉林大学 | Method for preparing black phosphorus under water self-elevating pressure |
| CN106586987B (en) * | 2016-11-04 | 2019-06-11 | 上海电力学院 | A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water |
| CN106744754A (en) * | 2016-11-14 | 2017-05-31 | 深圳大学 | A kind of red phosphorus preprocess method prepared for black phosphorus |
| CN109731587A (en) * | 2019-03-01 | 2019-05-10 | 中国科学院理化技术研究所 | A kind of two dimension non-metal optical catalytic composite materials and its preparation method and application |
| CN110040703B (en) * | 2019-04-23 | 2021-01-12 | 清华大学 | Preparation method and application of hydroxylated black phosphorus quantum dot water-based solution |
| CN111359640B (en) * | 2020-02-19 | 2022-06-21 | 东北师范大学 | Preparation method of multi-heterojunction titanium dioxide-bismuth vanadate-black phosphorus/red phosphorus composite film |
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