CN115895654A - Method for preparing purple phosphorus quantum dots, purple phosphorus quantum dots and application thereof - Google Patents
Method for preparing purple phosphorus quantum dots, purple phosphorus quantum dots and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to the technical field of nano materials, in particular to a method for preparing purple phosphorus quantum dots, the purple phosphorus quantum dots and application thereof. The method comprises the steps of firstly grinding the massive purple phosphorus in a mortar, then adding the grinded massive purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and then stripping the purple phosphorus along the layer by utilizing probe ultrasound. And then, longitudinally crushing the purple phosphorus quantum dots into quantum dots by water bath ultrasound, and finally obtaining the purple phosphorus quantum dots by a centrifugal separation technology. And the obtained purple phosphorus quantum dots are used as visible light response photocatalyst for solar photocatalytic water decomposition. By adopting the simple method, the high-quality purple phosphorus quantum dots which are ultrathin, uniform in size, uniform in dispersion and few in defects are obtained, so that the activity of the purple phosphorus-based narrow-band semiconductor material in photocatalytic water decomposition is improved. The preparation method is simple to operate, high in yield and easy for large-scale production. By changing the centrifugal rotating speed range, purple phosphorus quantum dots with different sizes and layers can be obtained, so that the band gap can be adjusted.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for preparing purple phosphorus quantum dots, the purple phosphorus quantum dots and application thereof.
Background
Solar energy has long been considered one of the most promising renewable energy sources as a free, clean, green and inexhaustible resource. First discovered in TiO in 1972 2 The electrode is used for decomposing water into hydrogen (H) gas by Ultraviolet (UV) irradiation 2 ) Has attracted considerable attention. To date, great efforts have been made to develop diverse semiconductor photocatalysts for efficient water decomposition. However, most conventional semiconductors such as TiO 2 Having a wide band gap of>3.2 eV), which means that uv light is necessary to activate its photocatalytic activity. In the solar spectrum, ultraviolet light accounts for only 5%, while visible light accounts for nearly 48% or so, and is not used to activate traditional semiconductor photocatalysts. In view of the utilization of solar energy, suitable materials as photocatalysts are required not only to have efficient solar-hydrogen conversion, but also to collect a broad spectrum of sunlight.
Phosphorus (P) accounts for 0.1% of the earth's crust and is one of the most abundant elements stored on earth. Recently, one of the P allotropes, purple phosphorus (VP) has been demonstrated to be a more stable layered semiconducting phosphorus allotrope than black phosphorus. The purple phosphorus has a layer-dependent tunable band gap from 1.68eV for bulk purple phosphorus to 2.02eV for monolayer purple phosphorus. Zero-dimensional (0D) quantum dots are another form of nanomaterial besides two-dimensional (2D) structures, having excellent electronic and optical properties due to their quantum confinement and edge effects. Although the purple phosphorus quantum dots are successfully obtained by an ultrasonic-assisted solvothermal method recently, the problems of complex operation, difficult control, multiple defects of products and the like exist in the preparation of the purple phosphorus quantum dots by the solvothermal method in practical application, and further research and development of the purple phosphorus quantum dots are restricted.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for preparing purple phosphorus quantum dots, the purple phosphorus quantum dots and application thereof, and aims to solve the problems of complex operation, difficult control, multiple defects of products and the like of the conventional method for preparing the purple phosphorus quantum dots (VPQDs).
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing purple phosphorus quantum dots, comprising the steps of:
mixing the massive purple phosphorus and an organic solvent in a mortar, and grinding for 0.5-5 hours to obtain a first dispersion liquid;
adding the first dispersion liquid into an organic solvent, and carrying out probe ultrasonic treatment for 0.1-10 hours under the constant temperature condition to obtain a second dispersion liquid;
performing water bath ultrasonic treatment on the second dispersion liquid for 0.5-10 hours to obtain a third dispersion liquid;
and carrying out centrifugal separation on the third dispersion liquid to obtain the purple phosphorus quantum dots.
Optionally, the organic solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, isopropanol, sec-butanol, isopropylamine and absolute ethanol.
Alternatively, the lumpy purple phosphorus and the organic solvent are mixed in a mortar in a mass ratio of 20.
Optionally, the first dispersion liquid is added into an organic solvent to make the concentration of the purple phosphorus be 0.01 umol/L-1 mol/L.
Optionally, the ultrasonic power of the probe is 5-100W; the constant temperature condition refers to a circulating condensation condition with the temperature of 1-10 ℃.
Optionally, the purple phosphorus quantum dots with the required size and the number of layers are obtained by controlling the centrifugal rotating speed.
Optionally, the size of the purple phosphorus quantum dot is 1-100 nm, and the thickness of the purple phosphorus quantum dot is 0.5-50 nm.
Optionally, the band gap of the purple phosphorus quantum dot is in the range of 0-3 ev.
The second aspect of the invention provides purple phosphorus quantum dots, wherein the purple phosphorus quantum dots are prepared by the method.
In a third aspect of the invention, an application of the purple phosphorus quantum dot as a photocatalyst in the field of solar photocatalytic water decomposition is provided.
Has the advantages that: the method comprises the steps of firstly grinding the massive purple phosphorus in a mortar, then adding the grinded massive purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and then stripping the purple phosphorus along the layer by utilizing probe ultrasound. And then, longitudinally crushing the purple phosphorus quantum dots into quantum dots by water bath ultrasound, and finally obtaining the purple phosphorus quantum dots by a centrifugal separation technology. The invention adopts the simple method to obtain the high-quality purple phosphorus quantum dots with ultra-thin thickness, uniform size, uniform dispersion and few defects, thereby improving the activity of the purple phosphorus-based narrow-band semiconductor material in photocatalytic water decomposition. The preparation method is simple to operate, high in yield and easy for large-scale production.
In the invention, centrifugal collection is adopted, and purple phosphorus quantum dots with different sizes and layers can be obtained by changing the range of centrifugal rotating speed. Namely, the size and the layer number of the purple phosphorus quantum dots are controllable, the size of the purple phosphorus quantum dots is 1-100 nm, and the thickness of the purple phosphorus quantum dots is 0.5-50 nm. The band gap of the purple phosphorus quantum dots can be adjusted according to the size and the number of layers of the purple phosphorus quantum dots, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. The obtained purple phosphorus quantum dots are firstly used as visible light response photocatalyst for solar photocatalytic water decomposition to prepare hydrogen.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing purple phosphorus quantum dots according to an embodiment of the present invention.
FIG. 2 is a high-power transmission electron microscope image and an atomic force microscope image of the purple phosphorus quantum dot prepared in example 1 of the present invention.
Detailed Description
The invention provides a method for preparing purple phosphorus quantum dots, purple phosphorus quantum dots and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
At present, almost no method for preparing the purple phosphorus quantum dot exists, and although the purple phosphorus quantum dot is successfully obtained by a solvothermal method recently reported, the problems of complex operation, difficult control, multiple defects of products and the like exist in the preparation of the purple phosphorus quantum dot by the solvothermal method in practical application, so that the further research and development of the purple phosphorus quantum dot are restricted. This is because the hydrothermal synthesis method (i.e., solvothermal method) requires high temperature and high pressure for a long time, which mainly breaks purple phosphorus into small-sized quantum dots by high temperature and high pressure, and thus the prepared quantum dots are severely oxidized and often have a large number of defect sites on the surface, resulting in low crystallinity thereof. And the hydrothermal synthesis method has low yield of the synthesized quantum dots and high preparation cost, and is not suitable for large-scale production.
Based on the method, the invention provides a simple and convenient preparation method of the purple phosphorus quantum dot, and the purple phosphorus quantum dot is firstly used in the field of photocatalysis to enrich the preparation method of the existing purple phosphorus quantum dot, so that the photocatalysis application of the purple phosphorus quantum dot is promoted. Specifically, the invention provides a grinding-assisted liquid-phase ultrasonic stripping method for preparing high-quality purple phosphorus quantum dots, aiming at the problems of complex operation, difficult control, multi-defect products and the like in the ultrasonic-assisted solvothermal method for preparing the purple phosphorus quantum dots, and the activity in photocatalytic water decomposition is seriously influenced. Zero-dimensional (0D) quantum dots are another nanomaterial than two-dimensional (2D) structures, having excellent electronic and optical properties due to their quantum structures and edge effects. The quantum dots can obtain a full spectrum of visible light, and the large surface area of the quantum dots can generate high catalytic activity, so that photo-generated charges can be rapidly moved to the surface, and the charge separation efficiency is remarkably improved. On the basis, the invention further improves and optimizes the activity of purple phosphorus quantum dots for photocatalytic water decomposition and hydrogen and oxygen evolution, and provides a new idea for customizing high-efficiency photocatalysts.
Referring to fig. 1, a method for preparing a purple phosphorus quantum dot provided by an embodiment of the present invention includes the steps of:
mixing the massive purple phosphorus and an organic solvent in a mortar, and grinding for 0.5-5 hours to obtain a first dispersion liquid;
adding the first dispersion liquid into an organic solvent, and carrying out probe ultrasonic treatment for 0.1-10 hours under the constant temperature condition to obtain a second dispersion liquid;
performing water bath ultrasonic treatment on the second dispersion liquid for 0.5-10 hours to obtain a third dispersion liquid;
and carrying out centrifugal separation on the third dispersion liquid to obtain the purple phosphorus quantum dots.
In this example, the lumpy purple phosphorus was first ground in a mortar, and then added to an appropriate amount of an organic solvent to prepare a dispersion liquid of a certain concentration, and then ultrasonically dispersed using a sharp ultrasonic probe under ice-cold conditions. And then, obtaining the purple phosphorus quantum dots by water bath ultrasound and centrifugal separation technology. The embodiment adopts the simple method to obtain the high-quality purple phosphorus quantum dots with ultra-thin thickness, uniform size, uniform dispersion and few defects, thereby improving the activity of the purple phosphorus-based narrow-band semiconductor material in photocatalytic water decomposition. The method solves the problem that the activity in photocatalytic water decomposition is seriously influenced due to the defects of complex operation, difficult control and multiple products in the process of preparing the purple phosphorus quantum dots by the existing solvothermal method. The preparation method is simple to operate, high in yield and easy for large-scale production.
The existing solvent thermal synthesis method mainly breaks the quantum dots into quantum dots by high temperature and high pressure. However, in this example, the ground purple phosphorus powder is mainly subjected to probe ultrasound, purple phosphorus is peeled along the layer by the probe ultrasound, and then the purple phosphorus is longitudinally crushed into purple phosphorus quantum dots by the water bath ultrasound.
In the embodiment, centrifugation is adopted to remove large purple phosphorus nanosheets, so that fine and uniform purple phosphorus quantum dots are obtained. By changing the range of centrifugal rotating speed, purple phosphorus quantum dots with different sizes and layers can be obtained. In this embodiment, the used centrifugation rotation speed interval may be 500 to 3000rpm, 3000 to 5000rpm, 5000 to 7000rpm, 7000 to 9000rpm, 9000 to 12000rpm, 12000 to 16000rpm, and each centrifugation time may be 2 to 120min. The size and the layer number of the purple phosphorus quantum dots are controllable, the size of the purple phosphorus quantum dots is 1-100 nm (such as 3-12 nm, 20-35 nm, 40-60 nm, 70-90 nm and the like), and the thickness of the purple phosphorus quantum dots is 0.5-50 nm (such as 0.5-3 nm, 5-15 nm, 20-30 nm, 30-45 nm and the like). The band gap of the purple phosphorus quantum dots can be adjusted according to the size and the number of layers of the purple phosphorus quantum dots, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. The purple phosphorus quantum dots are used as visible light response photocatalyst for solar photocatalytic water decomposition for hydrogen production.
In one embodiment, the organic solvent may be one or more of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, isopropyl alcohol, sec-butyl alcohol, isopropyl amine, anhydrous ethanol, and the like.
In one embodiment, the bulk purple phosphorus and the organic solvent are mixed in a mortar at a mass ratio of 20.
In one embodiment, the first dispersion is added to an organic solvent to make the concentration of the purple phosphorus be 0.01umol L-1 mol/L; further, the concentration is 1.66 mmol/L-0.1 mol/L; furthermore, the concentration is 1.66 mmol/L-16.66 mmol/L.
In one embodiment, the probe has an ultrasonic power of 5 to 100W.
In one embodiment, the isothermal condition refers to a cyclic condensation condition with a temperature of 1 to 10 ℃.
The embodiment of the invention provides a purple phosphorus quantum dot, which is prepared by the method provided by the embodiment of the invention.
The embodiment of the invention provides application of the purple phosphorus quantum dots as a narrow-band semiconductor photocatalyst in the field of solar photocatalytic water decomposition.
The purple phosphorus quantum dots prepared by the embodiment can be used in the field of photocatalysis as narrow-band semiconductors with unique optical and electronic properties.
The invention is further illustrated by the following specific examples.
Example 1
Mixing 30mg of lumpy purple phosphorus and 100ml of N-methylpyrrolidone in a mortar, and grinding for 0.5 hour to obtain a first dispersion liquid;
then, dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare purple phosphorus with the concentration of 0.1mol/L; performing probe ultrasonic treatment on the prepared dispersion liquid for 3 hours under the circulating condensation condition at the temperature of 5 ℃, wherein the ultrasonic power of the probe is 100W, and obtaining a second dispersion liquid;
then, carrying out water bath ultrasound on the second dispersion liquid for 2 hours, wherein the water bath ultrasound power is 400W, and obtaining a third dispersion liquid;
and centrifuging the third dispersion liquid at 12000rpm for 15min, and centrifuging the filtrate at 16000rpm for 15min to obtain the purple phosphorus quantum dots.
The test shows that the size of the prepared purple phosphorus quantum dot is 5.06nm, and the thickness is 0.7nm.
Fig. 2 is a high power transmission electron micrograph and an atomic force micrograph of the prepared purple phosphorus quantum dot, and it can be seen from fig. 2 that the size of the prepared purple phosphorus quantum dot is about 5nm, the layer thickness is about 0.7nm, which corresponds to a layer thickness of 1-2.
Example 2
Mixing 10mg of lumpy purple phosphorus and 50ml of N-methylpyrrolidone in a mortar, and grinding for 0.5 hour to obtain a first dispersion liquid;
then, dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare the purple phosphorus with the concentration of 6.66mmol/L; performing probe ultrasonic treatment on the prepared dispersion liquid for 3 hours under the circulating condensation condition at the temperature of 1 ℃, wherein the ultrasonic power of the probe is 100W, and obtaining a second dispersion liquid;
then carrying out water bath ultrasound on the second dispersion liquid for 2 hours, wherein the water bath ultrasound power is 400W, and obtaining a third dispersion liquid;
centrifuging the third dispersion liquid at 9000rpm for 15min, and centrifuging the filtrate at 12000rpm for 20min to obtain the purple phosphorus quantum dots.
The test shows that the size of the prepared purple phosphorus quantum dot is 8.58nm, and the thickness of the prepared purple phosphorus quantum dot is 1.89nm.
Example 3
Mixing 50mg of blocky purple phosphorus crystals and 100ml of N-methyl pyrrolidone in a mortar, and grinding for 1 hour to obtain a first dispersion liquid;
then, dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare purple phosphorus with the concentration of 16.66mmol/L; carrying out probe ultrasonic treatment on the prepared dispersion liquid for 4 hours under the circulating condensation condition at the temperature of 10 ℃, wherein the ultrasonic power of the probe is 80W, and obtaining a second dispersion liquid;
then carrying out water bath ultrasound on the second dispersion liquid for 2 hours, wherein the water bath ultrasound power is 400W, and obtaining a third dispersion liquid;
and centrifuging the third dispersion liquid at 7000rpm for 15min, and centrifuging the filtrate at 9000rpm for 10min to obtain the purple phosphorus quantum dots.
The purple phosphorus quantum dots prepared by the method have the size of 26.91nm and the thickness of 4.47nm.
Example 4
Mixing 5mg of the bulk purple phosphorus crystal and 100ml of N-methylpyrrolidone in a mortar, and grinding for 1.5 hours to obtain a first dispersion liquid;
then, dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare purple phosphorus with the concentration of 1.66mmol/L; carrying out probe ultrasonic treatment on the prepared dispersion liquid for 4 hours under the circulating condensation condition at the temperature of 5 ℃, wherein the ultrasonic power of a probe is 100W, and obtaining a second dispersion liquid;
then, carrying out water bath ultrasound on the second dispersion liquid for 2 hours, wherein the water bath ultrasound power is 400W, and obtaining a third dispersion liquid;
and centrifuging the third dispersion liquid at the rotation speed of 5000rpm for 15min, and centrifuging the filtrate at the rotation speed of 7000rpm for 15min to obtain the purple phosphorus quantum dots.
The purple phosphorus quantum dots prepared by the embodiment are tested to have the size of 55.80nm and the thickness of 8.64nm.
Application example 1
The photocatalytic water splitting performance of the purple phosphorus quantum dots prepared in the above examples was tested.
The photocatalytic reaction is evaluated by Pofely Labsolar-A6 online photocatalytic reaction equipment, a light source is a 300W Pofely PLS-SXE300D xenon lamp, and the reaction is carried out by a top irradiation method. The reactor was a 200 ml glass vessel sealed with quartz glass.
The specific photocatalytic test procedure was: weighing 50mg purple phosphorus quantum sample, dispersing in 120ml methanol water solution (methanol volume fraction is 20%), and smearingThe vacuum grease seals the reactor and then connects to the reaction system. The system was evacuated and prepared to begin the photocatalytic test without a change in pressure within 5 minutes. During the reaction, the reactant solution was kept at about 10 ℃ using a cooling water system. With the system set up, the product composition in the reactor was analyzed every 30 minutes, and the test apparatus was Fuli 9790II gas chromatography (equipped with molecular sieves)
Column and thermal conductivity detector, argon as carrier gas) to analyze the gas products.
The results of the photocatalytic experiments are shown in table 1 below:
TABLE 1 results of photocatalytic experiments
In summary, the invention provides a method for preparing a purple phosphorus quantum dot, a purple phosphorus quantum dot and an application thereof. The method comprises the steps of firstly grinding the massive purple phosphorus in a mortar, then adding the grinded massive purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and then stripping the purple phosphorus along the layer by utilizing probe ultrasound. And then, longitudinally crushing the purple phosphorus quantum dots by water bath ultrasound, and finally obtaining the purple phosphorus quantum dots by a centrifugal separation technology. The invention adopts the simple method to obtain the high-quality purple phosphorus quantum dots with ultra-thin thickness, uniform size, uniform dispersion and few defects, thereby improving the activity of the purple phosphorus-based narrow-band semiconductor material in photocatalytic water decomposition. The preparation method is simple to operate, high in yield and easy for large-scale production. In the invention, centrifugal collection is adopted, and purple phosphorus quantum dots with different sizes and layers can be obtained by changing the range of centrifugal rotating speed. Namely, the size and the layer number of the purple phosphorus quantum dots are controllable, the size of the purple phosphorus quantum dots is 3-12 nm, and the thickness of the purple phosphorus quantum dots is 0.5-3 nm. The band gap of the purple phosphorus quantum dots can be adjusted according to the size and the number of layers of the purple phosphorus quantum dots, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. The obtained purple phosphorus quantum dots are firstly used as visible light response photocatalyst for solar photocatalytic water decomposition to prepare hydrogen.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing purple phosphorus quantum dots is characterized by comprising the following steps:
mixing the massive purple phosphorus and an organic solvent in a mortar, and grinding for 0.5-5 hours to obtain a first dispersion liquid;
adding the first dispersion into an organic solvent, and carrying out probe ultrasonic treatment for 0.1-10 hours under the constant temperature condition to obtain a second dispersion;
performing water bath ultrasonic treatment on the second dispersion liquid for 0.5-10 hours to obtain a third dispersion liquid;
and carrying out centrifugal separation on the third dispersion liquid to obtain the purple phosphorus quantum dots.
2. The method for preparing purple phosphorus quantum dots according to claim 1, wherein the organic solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, isopropanol, sec-butanol, isopropylamine and absolute ethanol.
3. The method for preparing purple phosphorus quantum dots according to claim 1, wherein the bulk purple phosphorus and the organic solvent are mixed in a mortar at a mass/volume ratio of (5-50 mg) to (10-100 ml).
4. The method of claim 1, wherein the first dispersion is added to the organic solvent to make the concentration of the purple phosphorus 0.01 umol/L-1 mol/L.
5. The method for preparing the purple phosphorus quantum dots according to claim 1, wherein the ultrasonic power of the probe is 5-100W; the constant temperature condition refers to a circulating condensation condition with the temperature of 1-10 ℃.
6. The method for preparing purple phosphorus quantum dots according to claim 1, wherein the purple phosphorus quantum dots with required size and number of layers are obtained by controlling the centrifugal rotating speed.
7. The method for preparing the purple phosphorus quantum dot according to claim 1, wherein the size of the purple phosphorus quantum dot is 1-100 nm, and the thickness of the purple phosphorus quantum dot is 0.5-50 nm.
8. The method for preparing the purple phosphorus quantum dot according to claim 1, wherein the band gap of the purple phosphorus quantum dot is in the range of 0 to 3ev.
9. A purple phosphorus quantum dot, characterized in that, the purple phosphorus quantum dot is prepared by the method of any one of claims 1 to 8.
10. The use of the purple phosphorus quantum dot of claim 9 as a photocatalyst in the field of solar photocatalytic water splitting.
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