CN115895654B - 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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- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 68
- 239000011574 phosphorus Substances 0.000 claims abstract description 68
- 239000002096 quantum dot Substances 0.000 claims abstract description 56
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 claims abstract description 23
- 239000000523 sample Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 11
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- 238000002360 preparation method Methods 0.000 abstract description 10
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- 238000000354 decomposition reaction Methods 0.000 abstract description 6
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- 239000002086 nanomaterial Substances 0.000 abstract description 4
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- 238000004729 solvothermal method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 a purple phosphorus quantum dot, the purple phosphorus quantum dot and application thereof. Firstly, grinding block-shaped purple phosphorus in a mortar, then adding the grinded block-shaped purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and peeling the purple phosphorus along the layer by utilizing probe ultrasonic. And then longitudinally crushing the mixture into quantum dots by water bath ultrasonic treatment, 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 photocatalysts for solar photocatalytic water splitting. By adopting the simple method, the ultra-thin high-quality purple phosphorus quantum dots with uniform size, uniform dispersion and few defects are obtained, 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. Violet phosphor quantum dots with different sizes and layers can be obtained by changing the centrifugal rotating speed range, so that the band gap is adjustable.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for preparing a purple phosphorus quantum dot, the purple phosphorus quantum dot 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. Since 1972, it was first discovered that TiO 2 After decomposing water on the electrode under Ultraviolet (UV) light irradiation, the decomposition of water into hydrogen (H) 2 ) The semiconductor photocatalyst of (2) has attracted considerable attention. Up to now, great efforts have been made to develop various semiconductor photocatalysts for efficiently decomposing water. However, most conventional semiconductors such as TiO 2 Has wide band gap>3.2 eV), which means that ultraviolet light is necessary to activate its photocatalytic activity. In the solar spectrum, ultraviolet light only occupies 5%, while visible light occupies about 48%, which is not usedThe conventional semiconductor photocatalyst is activated. Suitable materials as photocatalysts are required not only to have efficient solar-hydrogen conversion, but also to collect a broad spectrum of sunlight in view of solar energy utilization.
Phosphorus (P) accounts for 0.1% of the crust, and is one of the most abundant elements stored on earth. Recently, one of the allotropes of P, violet Phosphorus (VP), has been demonstrated to be a more stable layered semiconductor phosphorus allotrope than black phosphorus. The violet phosphorus has a layer-dependent tunable band gap ranging from 1.68eV for bulk violet phosphorus to 2.02eV for single layer violet phosphorus. Zero-dimensional (0D) quantum dots are another form of nanomaterial other than two-dimensional (2D) structures that have excellent electronic and optical properties due to their quantum confinement and edge effects. Although the ultrasonic assisted solvothermal method is reported to be successful in obtaining the purple phosphorus quantum dots recently, the solvothermal method for preparing the purple phosphorus quantum dots in practical application has the problems of complex operation, difficult control, multiple defects of products and the like, and further research and development of the purple phosphorus quantum dots are restricted.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing a purple phosphorus quantum dot, the purple phosphorus quantum dot and application thereof, and aims to solve the problems of complex operation, difficult control, multiple defects of products and the like of the existing method for preparing the purple phosphorus quantum dot (VPQD).
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a violet phosphorus quantum dot, comprising the steps of:
mixing block 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 performing probe ultrasound 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.
Optionally, the block purple phosphorus and the organic solvent are mixed in a mortar according to the mass ratio of 20:1-1:20.
Optionally, the first dispersion is added to an organic solvent so that the concentration of purple phosphorus is 0.01umol/L to 1mol/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 layer number 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 range of the purple phosphorus quantum dot is 0-3 ev.
In a second aspect of the invention, a purple phosphorus quantum dot is provided, wherein the purple phosphorus quantum dot is prepared by the method of the invention.
In a third aspect, the invention provides an application of the purple phosphorus quantum dot as a photocatalyst in the field of solar photocatalytic water splitting.
The beneficial effects are that: firstly, grinding block-shaped purple phosphorus in a mortar, then adding the grinded block-shaped purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and peeling the purple phosphorus along the layer by utilizing probe ultrasonic. And then longitudinally crushing the mixture into quantum dots by water bath ultrasonic treatment, and finally obtaining the purple phosphorus quantum dots by a centrifugal separation technology. The invention adopts the simple method to obtain the ultra-thin, uniform-size, uniformly dispersed and low-defect high-quality purple phosphorus quantum dots, 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.
According to the invention, through adopting centrifugal collection and changing the centrifugal rotating speed range, the purple phosphorus quantum dots with different sizes and layers can be obtained. 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. According to the size and the layer number of the purple phosphorus quantum dots, the band gap of the purple phosphorus quantum dots can be adjusted, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. And the obtained purple phosphorus quantum dots are used as visible light response photocatalysts for the first time and are used for preparing hydrogen by solar photocatalytic water splitting.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a violet phosphorus quantum dot 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 violet phosphorus quantum dot prepared in example 1 of the present invention.
Detailed Description
The invention provides a method for preparing a purple phosphorus quantum dot, the purple phosphorus quantum dot and application thereof, and the method is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
At present, the method for preparing the purple phosphorus quantum dot is almost absent, and although the purple phosphorus quantum dot is successfully obtained by a solvothermal method recently, the solvothermal method for preparing the purple phosphorus quantum dot in practical application has the problems of complex operation, difficult control, multiple defects of products and the like, and further research and development are restricted. This is because the hydrothermal synthesis method (i.e., solvothermal method) requires a long time of preparation at high temperature and high pressure, which breaks up the purple phosphorus into small-sized quantum dots mainly 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 a low crystallinity. And the yield of the synthesized quantum dots by the hydrothermal synthesis method is low, the preparation cost is high, and the large-scale production is not suitable.
Based on the method, the invention provides a simple preparation method of the purple phosphorus quantum dot, and the purple phosphorus quantum dot is firstly used in the field of photocatalysis so as to enrich the current preparation method of the purple phosphorus quantum dot, thereby promoting the photocatalysis application of the purple phosphorus quantum dot. Specifically, aiming at the problems of complex operation, difficult control, multiple defects of products and the like in the preparation of the purple phosphorus quantum dots by an ultrasonic auxiliary solvothermal method, the activity in photocatalytic water decomposition is seriously influenced, and the preparation of the high-quality purple phosphorus quantum dots by a grinding auxiliary liquid phase ultrasonic stripping method is provided. Zero-dimensional (0D) quantum dots are another nanomaterial other than two-dimensional (2D) structures, which have excellent electronic and optical properties due to their quantum structures and edge effects. The quantum dots can obtain the full spectrum of visible light, and the larger surface area of the quantum dots can generate higher catalytic activity, so that photo-generated charges can be quickly moved to the surface, and the charge separation efficiency is obviously improved. On the basis, the invention further improves and optimizes the photocatalytic water splitting hydrogen and oxygen evolution activity of the purple phosphorus quantum dots, and provides a new idea for customizing the high-efficiency photocatalyst.
Referring to fig. 1, the method for preparing a purple phosphorus quantum dot according to the embodiment of the present invention includes the following steps:
mixing block 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 performing probe ultrasound 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, block purple phosphorus was first ground in a mortar, and then added to an appropriate amount of an organic solvent to prepare a dispersion of a certain concentration, and then dispersed ultrasonically under ice-cold conditions using a tip ultrasonic probe. And then carrying out water bath ultrasonic treatment and centrifugal separation technology to obtain the purple phosphorus quantum dots. The embodiment adopts the simple method to obtain the ultra-thin, uniform-size, uniformly dispersed and low-defect high-quality purple phosphorus quantum dots, thereby improving the activity of the purple phosphorus-based narrow-band semiconductor material in photocatalytic water decomposition. The method solves the problems that the prior solvothermal method has complex operation, difficult control and multiple defects of products in the process of preparing the purple phosphorus quantum dots, and seriously affects the activity in photocatalytic water splitting. The preparation method of the embodiment is simple to operate, high in yield and easy for large-scale production.
The existing solvothermal synthesis method is mainly used for crushing the solvent into quantum dots through high temperature and high pressure. However, in this embodiment, the milled violet phosphorus powder is subjected to probe ultrasound, the layer is peeled off by using probe ultrasound, and then the layer is longitudinally broken into the violet phosphorus quantum dots by water bath ultrasound.
In the embodiment, centrifugation is adopted to remove large blocks of purple phosphorus nano-sheets, so that tiny and uniform purple phosphorus quantum dots are obtained. Through changing the centrifugal rotating speed range, the purple phosphorus quantum dots with different sizes and layers can be obtained. In this example, the centrifugal speed ranges used may be 500 to 3000rpm, 3000 to 5000rpm, 5000 to 7000rpm, 7000 to 9000rpm, 9000 to 12000rpm, 12000 to 16000rpm, and the centrifugal time may be 2 to 120 minutes each time. 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 is 0.5-50 nm (such as 0.5-3 nm, 5-15 nm, 20-30 nm, 30-45 nm and the like). According to the size and the layer number of the purple phosphorus quantum dots, the band gap of the purple phosphorus quantum dots can be adjusted, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. And the obtained purple phosphorus quantum dots are used as visible light response photocatalysts for the first time and are used for preparing hydrogen by solar photocatalytic water splitting.
In one embodiment, the organic solvent may be one or more of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, isopropanol, sec-butanol, isopropylamine, absolute ethanol, and the like.
In one embodiment, the block purple phosphorus and the organic solvent are mixed in a mortar in a mass ratio of 20:1 to 1:20.
In one embodiment, the first dispersion is added to an organic solvent to provide a concentration of violet phosphorus of 0.01umolL to 1mol/L; further, the concentration is 1.66mmol/L to 0.1mol/L; further, the concentration is 1.66mmol/L to 16.66mmol/L.
In one embodiment, the probe ultrasonic power is 5-100W.
In one embodiment, the constant temperature condition refers to a cyclic condensation condition having a temperature of 1 to 10 ℃.
The embodiment of the invention provides a purple phosphorus quantum dot, which is prepared by adopting the method disclosed by the embodiment of the invention.
The embodiment of the invention provides application of the purple phosphorus quantum dot serving as a narrow-band semiconductor photocatalyst in the field of solar photocatalytic water splitting.
The purple phosphorus quantum dot prepared by the embodiment can be used as a narrow-band semiconductor with unique optical and electronic characteristics in the field of photocatalysis.
The invention is further illustrated by the following examples.
Example 1
30mg of block purple phosphorus and 100ml of N-methylpyrrolidone were mixed in a mortar and ground for 0.5 hour to obtain a first dispersion;
then dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare the concentration of the purple phosphorus of 0.1mol/L; carrying out probe ultrasound on the prepared dispersion liquid for 3 hours under the cyclic condensation condition of 5 ℃ and the probe ultrasound power is 100W to obtain a second dispersion liquid;
then carrying out water bath ultrasonic treatment on the second dispersion liquid for 2 hours, wherein the ultrasonic power of the water bath is 400W, so as to obtain a third dispersion liquid;
and centrifuging the third dispersion liquid at 12000rpm for 15min, and then taking filtrate and centrifuging at 16000rpm for 15min to obtain the purple phosphorus quantum dots.
Through testing, 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 microscope image and an atomic force microscope image of the prepared violet phosphorus quantum dot, and as can be seen from fig. 2, the size of the prepared violet phosphorus quantum dot is about 5nm, and the layer thickness is about 0.7nm, corresponding to 1-2 layer thickness.
Example 2
10mg of block purple phosphorus and 50ml of N-methylpyrrolidone were mixed in a mortar and ground for 0.5 hour to obtain a first dispersion;
then dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare the purple phosphorus with the concentration of 6.66mmol/L; carrying out probe ultrasound on the prepared dispersion liquid for 3 hours under the cyclic condensation condition of 1 ℃ and the probe ultrasound power is 100W to obtain a second dispersion liquid;
then carrying out water bath ultrasonic treatment on the second dispersion liquid for 2 hours, wherein the ultrasonic power of the water bath is 400W, so as to obtain a third dispersion liquid;
and centrifuging the third dispersion liquid at 9000rpm for 15min, and then taking filtrate and centrifuging at 12000rpm for 20min to obtain the purple phosphorus quantum dots.
Through testing, the size of the prepared purple phosphorus quantum dot is 8.58nm, and the thickness is 1.89nm.
Example 3
50mg of block purple phosphorus crystals and 100ml of N-methylpyrrolidone were mixed in a mortar and ground for 1 hour to obtain a first dispersion;
then dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare the purple phosphorus with the concentration of 16.66mmol/L; carrying out probe ultrasound on the prepared dispersion liquid for 4 hours under the cyclic condensation condition of 10 ℃, wherein the ultrasonic power of the probe is 80W, so as to obtain a second dispersion liquid;
then carrying out water bath ultrasonic treatment on the second dispersion liquid for 2 hours, wherein the ultrasonic power of the water bath is 400W, so as to obtain a third dispersion liquid;
and centrifuging the third dispersion liquid at 7000rpm for 15min, and then centrifuging the filtrate at 9000rpm for 10min to obtain the purple phosphorus quantum dots.
Through tests, the size of the purple phosphorus quantum dot prepared in the embodiment is 26.91nm, and the thickness is 4.47nm.
Example 4
5mg of block purple phosphorus crystals and 100ml of N-methylpyrrolidone were mixed in a mortar and ground for 1.5 hours to obtain a first dispersion;
then dispersing the first dispersion liquid into N-methyl pyrrolidone to prepare the concentration of the purple phosphorus of 1.66mmol/L; carrying out probe ultrasound on the prepared dispersion liquid for 4 hours under the cyclic condensation condition of 5 ℃ and the ultrasonic power of the probe is 100W to obtain a second dispersion liquid;
then carrying out water bath ultrasonic treatment on the second dispersion liquid for 2 hours, wherein the ultrasonic power of the water bath is 400W, so as to obtain a third dispersion liquid;
and centrifuging the third dispersion liquid at 5000rpm for 15min, and then taking filtrate and centrifuging at 7000rpm for 15min to obtain the purple phosphorus quantum dots.
Through tests, the size of the purple phosphorus quantum dot prepared in the embodiment is 55.80nm, and the thickness is 8.64nm.
Application example 1
The photocatalytic water splitting performance of the violet phosphorus quantum dots prepared in the above examples was tested.
The photocatalytic reaction was evaluated by a Porphy's Labsolar-A6 on-line photocatalytic reaction device, the light source was a 300W Porphy's PLS-SXE300D xenon lamp, and the reaction was performed by a top irradiation method. The reactor was a 200 ml glass vessel, which was sealed with quartz glass.
The specific photocatalysis test steps are as follows: 50mg of the purple phosphorus quantum dot sample was weighed and dispersed in 120ml of an aqueous methanol solution (volume fraction of methanol: 20%), and then the reactor was sealed by applying vacuum grease, and then connected to a reaction system. The system was evacuated and ready to begin photocatalytic testing without pressure change for 5 minutes. During the reaction, the reactant solution was maintained at around 10 ℃ using a cooling water system. The product components in the reactor were analyzed every 30 minutes by a system setup, the test instrument was a fuli 9790II gas chromatograph (equipped with molecular sievesColumn and thermal conductivity detector, argon as carrier gas) to analyze the gas product.
The photocatalytic test results are shown in table 1 below:
TABLE 1 photocatalytic experimental results
In summary, the invention provides a method for preparing a purple phosphorus quantum dot, the purple phosphorus quantum dot and application thereof. Firstly, grinding block-shaped purple phosphorus in a mortar, then adding the grinded block-shaped purple phosphorus into a proper amount of organic solvent to prepare dispersion liquid with a certain concentration, and peeling the purple phosphorus along the layer by utilizing probe ultrasonic. And then longitudinally crushing the mixture into quantum dots by water bath ultrasonic treatment, and finally obtaining the purple phosphorus quantum dots by a centrifugal separation technology. The invention adopts the simple method to obtain the ultra-thin, uniform-size, uniformly dispersed and low-defect high-quality purple phosphorus quantum dots, 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. According to the invention, through adopting centrifugal collection and changing the centrifugal rotating speed range, the purple phosphorus quantum dots with different sizes and layers can be obtained. 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. According to the size and the layer number of the purple phosphorus quantum dots, the band gap of the purple phosphorus quantum dots can be adjusted, and the band gap range of the purple phosphorus quantum dots can be 1-3 ev. And the obtained purple phosphorus quantum dots are used as visible light response photocatalysts for the first time and are used for preparing hydrogen by solar photocatalytic water splitting.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A method for preparing a violet phosphorus quantum dot, comprising the steps of:
mixing block 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 performing probe ultrasound 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.
2. The method of preparing violet 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, dimethylsulfoxide, isopropanol, sec-butanol, isopropylamine, and absolute ethanol.
3. The method for preparing the purple phosphorus quantum dots according to claim 1, wherein the bulk purple phosphorus and the organic solvent are mixed in a mortar according to a mass-volume ratio of (5-50 mg) (10-100 mL).
4. The method for preparing the violet phosphorus quantum dot according to claim 1, wherein the first dispersion liquid is added to an organic solvent so that the concentration of violet phosphorus is 0.01 μmol/L to 1mol/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 the purple phosphorus quantum dots according to claim 1, wherein the purple phosphorus quantum dots with the required size and layer number are obtained by controlling the centrifugal rotation speed.
7. The method for preparing the purple phosphorus quantum dots according to claim 1, wherein 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.
8. The method of preparing a violet phosphorus quantum dot according to claim 1, wherein the band gap of the violet phosphorus quantum dot is in the range of 0 to 3ev.
9. The purple phosphorus quantum dot is characterized in that the purple phosphorus quantum dot is prepared by the method of any one of claims 1 to 8.
10. Use of the violet phosphorus quantum dot of claim 9 as a photocatalyst in the field of solar photocatalytic water splitting.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211481813.8A CN115895654B (en) | 2022-11-24 | 2022-11-24 | Method for preparing purple phosphorus quantum dots, purple phosphorus quantum dots and application thereof |
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