CN113980677A - g-C3N4Quantum dot and preparation method thereof - Google Patents
g-C3N4Quantum dot and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002096 quantum dot Substances 0.000 claims abstract description 95
- 239000002243 precursor Substances 0.000 claims abstract description 74
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 68
- 239000000843 powder Substances 0.000 claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000013590 bulk material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 abstract description 10
- 230000001788 irregular Effects 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 238000001816 cooling Methods 0.000 description 17
- 238000003917 TEM image Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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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
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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Abstract
The invention discloses a g-C3N4The preparation method of quantum dot comprises the steps of firstly, controlling the appearance of melamine by a hydrothermal method, adding urea in hydrothermal reaction to convert the appearance of irregular granular melamine into a rod-like melamine precursor, and then calcining the melamine precursor with the special structure in air to obtain the quantum dot containing a large amount of g-C3N4g-C of fibres3N4Powder, finally breaking the g-C by ultrasonication with a cell disruptor3N4The fibres give g-C3N4And (4) quantum dots. The g-C3N4The preparation and purification process of the quantum dots is simple, and the raw materials are cheap and easy to obtainThe quantum dots are easy to disperse in aqueous solution, have good fluorescence characteristics, and have wide application prospects in the fields of fluorescence sensors and photocatalysis.
Description
Technical Field
The invention belongs to the field of quantum dot preparation, and particularly relates to g-C3N4Quantum dots and methods of making the same.
Background
g-C3N4Is a metal-free organic semiconductor with a band gap of 2.7eV and has a two-dimensional layered structure similar to graphite. g-C3N4Carbon and nitrogen atoms in the layers are hybridized by sp2, have pi-conjugated electronic structures, and are bonded by van der waals force between the layers. Thus, g-C3N4The block material can be stripped into two-dimensional nanosheets, so that specific surface junctions are increased, band gaps are adjusted, and the block material has wide application prospects in the fields of photocatalysis, water photolysis, photoelectric sensors and the like. In g-C3N4The quantum dots are obtained by further reducing the size on the basis of the two-dimensional nanosheets, so that the quantum dots have unique structure, optical and electrical properties. g-C3N4The quantum dots have the advantages of strong photobleaching resistance, good biocompatibility, low toxicity and the like, so that the quantum dots can be widely applied to the fields of cell imaging, ion detection and the like. g-C3N4More catalytic active sites of the quantum dots enable the quantum dots to have excellent visible light photocatalytic performance. Thus, g-C3N4The preparation of quantum dots has become a focus of attention.
Up to now, g-C is prepared by a top-down hydrothermal chemical shearing method, a liquid phase ultrasonic stripping method, a secondary high-temperature calcination decomposition method and the like3N4Bulk material size reduction to g-C3N4Quantum dots; heating the precursor solution from bottom to top to carry out solvent thermal reaction to obtain g-C3N4And (4) quantum dots. The methods have the defects of complex operation process, time-consuming purification process, low yield and the like in the process of preparing the quantum dots, and severely limit the g-C3N4Application of quantum dots. To solve g-C3N4The problems existing in the preparation process of the quantum dots require the development of a preparation method which has simple operation and purification process and high yield.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned prior artDisadvantages of the technique, providing a g-C3N4The quantum dot and the preparation method thereof solve the problems of complex operation process, time-consuming purification process and low yield and defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
g-C3N4The preparation method of the quantum dot comprises the following steps:
step 1, dissolving urea in deionized water to obtain a precursor solution;
step 2, adding melamine into the precursor solution, mixing, performing ultrasonic treatment, and performing magnetic stirring after ultrasonic treatment to obtain melamine dispersion liquid;
step 3, carrying out hydrothermal reaction on the melamine dispersion liquid to obtain a reaction system;
step 4, washing the reaction system by water and ethanol, and then separating and purifying to obtain melamine precursor powder; the microstructure of the melamine precursor powder is rod-shaped and lamellar;
step 5, putting the melamine precursor powder into a porcelain boat or an alumina crucible, wrapping the porcelain boat or the alumina crucible with an aluminum foil, calcining in an air environment, and calcining to obtain g-C3N4A bulk material; g to C3N4Dispersing the block material in a solvent, and performing ultrasonic crushing by a cell crushing instrument to obtain yellow turbid liquid;
step 6, purifying the yellow suspension by centrifugal separation, and drying the centrifugal product in vacuum to obtain g-C3N4And (4) quantum dots.
The invention is further improved in that:
preferably, in step 2, the mass ratio of melamine to urea is 1: 1.
Preferably, in the step 2, the ultrasonic treatment time is 20-60min, and the magnetic stirring time is more than 30 min.
Preferably, in the step 3, the hydrothermal reaction temperature is 160-200 ℃ and the hydrothermal reaction time is 18-24 h.
Preferably, in the step 5, the calcination temperature is 500-600 ℃, the heating rate is 10-20 ℃/min, the heat preservation time is 1-5h, and the temperature is naturally reduced after heat preservation.
Preferably, in step 5, the solvent is deionized water, absolute ethyl alcohol, N-dimethylformamide, N-methylpyrrolidone or isopropanol.
Preferably, in step 5, the power of the cell crusher during ultrasonic crushing is 10-1800W, the crushing time is 10-60 min, and the crushing temperature is 0-10 ℃.
Preferably, in the step 6, the vacuum drying temperature is 60-100 ℃, and the vacuum drying time is 12-24 h.
g-C prepared by any one of the preparation methods3N4Quantum dots, g-C3N4The quantum dots are in a wafer shape, and the particle size is 5-15 nm.
Preferably, said g-C3N4The quantum dots have the strongest fluorescence emission at 430nm under the excitation of 325nm light.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a g-C3N4The preparation method of the quantum dots comprises the steps of firstly, controlling the appearance of melamine by a hydrothermal method, adding urea in hydrothermal reaction to convert the appearance of irregular granular melamine into a rod-shaped melamine precursor, and then calcining the melamine precursor with the special structure in air to obtain the quantum dots containing a large amount of g-C3N4g-C of fibres3N4Powder, finally breaking the g-C by ultrasonication with a cell disruptor3N4The fibres give g-C3N4And (4) quantum dots. The invention controls the g-C obtained after calcination by controlling the appearance of the melamine precursor for the first time3N4Such that g-C after calcination3N4Presenting a rod-like structure. g-C3N4The rod has smooth surface and a large amount of g-C distributed in the rod3N4And (3) nano fibers. g-C of these fibers during sonication with a cell disruptor3N4The fiber is easily broken into g-C3N4And (4) quantum dots. The g-C3N4The preparation and purification processes of the quantum dots are simple, the raw materials are cheap and easy to obtain, the quantum dots are easy to disperse in aqueous solution, and the quantum dots have good fluorescence characteristics and wide application prospects in the fields of fluorescence sensors and photocatalysis. g-C provided by the invention3N4The preparation method of the quantum dots has the advantages of simple preparation process, short time consumption and low cost, and is suitable for the fields of photocatalysis, fluorescence sensors and the like.
The invention also discloses a g-C3N4The quantum dot is easy to disperse in aqueous solution, has good fluorescence characteristic, and has wide application prospect in the fields of fluorescence sensors and photocatalysis.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of melamine in example 1 of the present invention;
FIG. 2 is an SEM photograph of a melamine precursor obtained in example 1 of the present invention;
FIG. 3 is an X-ray diffraction (XRD) pattern of melamine and a melamine precursor obtained after hydrothermal treatment in example 1 of the present invention;
FIG. 4 shows g-C obtained in example 1 of the present invention3N4SEM image of powder
FIG. 5 shows g-C obtained after disruption in a cell disruptor in example 1 of the present invention3N4A Transmission Electron Microscope (TEM) image of the powder;
FIG. 6 shows g-C obtained after disruption in a cell disruptor in example 1 of the present invention3N4Powder and g-C3N4XRD patterns of quantum dots;
FIG. 7 shows g-C obtained in example 1 of the present invention3N4A TEM image of the quantum dots;
FIG. 8 shows g-C obtained in example of the present invention3N4Fluorescence emission spectrograms of the quantum dots;
FIG. 9 shows g-C obtained in example 2 of the present invention3N4A TEM image of the quantum dots;
FIG. 10 shows g-C obtained in example 3 of the present invention3N4TEM image of quantum dots。
FIG. 11 shows g-C obtained in example 4 of the present invention3N4TEM images of quantum dots.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
in the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly and encompass, for example, both fixed and removable connections; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Graphite phase g-C3N4Quantum dots of said g-C3N4The particle size of the quantum dots is 5-8nm, and the quantum dots are uniformly dispersed.
The g to C3N4The preparation method of the quantum dot comprises the following steps:
step 1, dissolving urea in deionized water to obtain a precursor solution;
step 2, adding melamine into the solution obtained in the step 1, wherein the mass ratio of the melamine to the urea is 1: 1; carrying out ultrasonic treatment after mixing, wherein the ultrasonic time is 20-60min, and carrying out magnetic stirring after ultrasonic treatment; magnetic stirring is carried out for not less than 30 minutes to obtain melamine dispersion liquid;
step 3, transferring the melamine dispersion liquid obtained in the step 2 into a reaction kettle, and heating for hydrothermal reaction; the filling rate of the reaction kettle is less than 90 percent, the capacity of the reaction kettle is preferably 100mL, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 18-24 hours. Preferably, the reaction temperature is 180 ℃ and the reaction time is 20 hours, so as to obtain a reaction system.
And 4, after the hydrothermal reaction is finished, repeatedly centrifugally cleaning the reaction system by using deionized water and ethanol, separating and purifying to obtain melamine precursor powder, wherein the obtained melamine precursor powder is rod-shaped and lamellar.
Step 5, putting the melamine powder obtained in the step 4 into a muffle furnace, and calcining in air to obtain g-C3N4A bulk material. During calcination, the melamine precursor is placed in a porcelain boat or an alumina crucible, and the porcelain boat and the crucible are wrapped by aluminum foil. Calcining in air at a temperature rise rate of 10-20 deg.C/min, at a temperature of 500-600 deg.C for 1-5 hr, and naturally cooling. g-C obtained3N4The bulk material contains a large amount of g-C3N4A fiber.
Preferably, the calcining temperature rise rate is 15 ℃/min, the holding temperature is 550 ℃, and the holding time is 4 hours.
Subjecting the g-C obtained in step 53N4Dispersing the block material in a solvent, and performing ice-bath ultrasonic crushing by using a cell crusher to obtain yellow turbid liquid;
in the scheme, the dispersion solvent used in the cell disruption instrument is deionized water, absolute ethyl alcohol, N-dimethylformamide, N-methylpyrrolidone or isopropanol. Preferably, N-dimethylformamide is selected as the ultrasonic dispersion solvent.
In the scheme, the power of the cell crusher during crushing is 10-1800W, the crushing time is 10-60 min, and the crushing temperature is 0-10 ℃.
Preferably, the ultrasonic crushing power is 500-.
Step 7, separating and purifying the yellow suspension obtained in the step 6 to obtain g-C3N4And (4) quantum dots. In the above scheme, the step of separating and purifying the suspension comprises: transferring the suspension into a 50mL centrifuge tube, centrifuging at 500rmp for 3min, and removing large particles to obtain light yellow suspension. Transferring the light yellow suspension obtained in the previous step into a 50mL centrifuge tube, centrifuging at 1500rmp for 3min to remove secondary large particles to obtain light yellow suspension, centrifuging at 8000rmp for 5min to obtain light yellow solid, and vacuum drying at 80 deg.C for 24 hr to obtain light yellow powdered g-C3N4And (4) quantum dots.
Preferably, the rotation speed during centrifugal cleaning is 800rmp, the centrifugal time is 5 minutes, the drying temperature is 80 ℃, and the drying time is 24 hours.
g-C prepared according to the above scheme3N4The quantum dots are disc-shaped, the particle size is 5-15nm, the specific surface area is large, and the number of active sites is large.
g-C prepared by the scheme3N4The quantum dots have the strongest fluorescence emission at 430nm under the excitation of light with the wavelength of 325nm, g-C3N4The quantum dots have good fluorescent properties.
According to the invention, the appearance of melamine is changed from irregular particles into a rod-shaped structure by a hydrothermal method, and the rod-shaped structure can limit or induce the melamine in the rod-shaped melamine rod to be pyrolyzed and polycondensed into a nano-fiber shape in the calcining process. Therefore, the rod-shaped melamine precursor presents a structure with a smooth surface and a large amount of g-C3N4 fibers distributed inside after being sintered.
The following is further illustrated with reference to specific examples:
example 1
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. weighing 4g of urea, dissolving in 50mL of deionized water, and stirring to obtain a colorless clear solution;
2. weighing 4g of irregular granular melamine (shown in figure 1) and adding the irregular granular melamine into the urea solution obtained in the step 1, and performing magnetic stirring for 1 hour after performing ultrasonic treatment for 30 minutes;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 100ml polytetrafluoroethylene lining, preserving the heat at 180 ℃ for 24h, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped melamine precursor, wherein the appearance of the white rod-shaped melamine precursor is shown in a figure (2). The XRD patterns of the melamine powder before and after hydrothermal treatment are shown in fig. 3.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at a heating rate of 15 ℃ per minute to 550 ℃, keeping the temperature for 4 hours, and naturally cooling to obtain yellow powdery g-C3N4. FIG. 4 is a yellow powder g-C3N4SEM image of (5), from which yellow powdery g-C was observed3N4Has a tubular shape, smooth outer wall, and a large amount of g-C in the tube3N4And (3) nano fibers.
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing into 50mL of N, N-dimethylformamide, and carrying out ultrasonic treatment by using a cell disruptor, wherein the ultrasonic disruption power is 700W, the ultrasonic disruption time is 30 minutes, and the ultrasonic disruption temperature is 0 ℃. FIG. 5 shows the g-C obtained after disruption by a cell disruptor3N4A Transmission Electron Microscope (TEM) image of the powder; FIG. 6 shows the g-C obtained after disruption by a cell disruptor3N4Powder and g-C3N4XRD patterns of quantum dots; FIG. 7 shows the result is g-C3N4TEM images of quantum dots.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 80 deg.C for 24 hr to obtain light yellow powder g-C3N4And (4) quantum dots. g-C obtained3N4The quantum dots have good luminescence property, and the fluorescence spectrum of the quantum dots is shown in figure 8.
FIG. 1 is a scanning electron microscope picture of melamine particles according to an example of the invention, from which it is seen that the particles are randomly granular.
Fig. 2 is a scanning electron microscope image of the melamine precursor obtained in the example of the present invention, and it can be seen from the image that the irregular melamine particles are transformed into rod-like morphology after hydrothermal treatment.
FIG. 3 is an X-ray diffraction diagram of melamine and a melamine precursor obtained after treatment by a hydrothermal method in an example of the present invention.
FIG. 4 shows g-C obtained in example of the present invention3N4SEM image of powder, and g-C was observed as a yellow powder3N4Has a tubular shape, smooth outer wall, and a large amount of g-C in the tube3N4And (3) nano fibers.
FIG. 5 shows the g-C obtained after disruption by a cell disruptor in an embodiment of the invention3N4Transmission electron microscopy of the powder, from which a large amount of g-C is seen3N4And (3) nano fibers.
FIG. 6 shows the g-C obtained after disruption by a cell disruptor in an embodiment of the invention3N4Powder and g-C3N4XRD pattern of quantum dots, g-C3N4g-C obtained by ultrasonic treatment of nano-fiber3N4The crystal structure of the quantum dots is not changed.
FIG. 7 shows g-C obtained in example of the present invention3N4TEM image of quantum dots, resulting g-C3N4The quantum dots are uniform in size and distribution.
FIG. 8 shows g-C obtained in example of the present invention3N4The fluorescence emission spectrum of the quantum dot shows that the quantum dot emits well at 428nm under the excitation of light with the wavelength of 325nm, which indicates that the obtained quantum dot has good fluorescence performance.
Example 2
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 30 minutes and then carrying out magnetic stirring for 1 hour;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 180 ℃ for 18h, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at a heating rate of 15 ℃ per minute to 550 ℃ for 2 hours, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing into 50ml of N, N-dimethylformamide, and carrying out ultrasonic treatment by using a cell disruptor, wherein the ultrasonic disruption power is 500W, the ultrasonic disruption time is 40 minutes, and the ultrasonic disruption temperature is 0 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 80 deg.C for 24 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
Referring to fig. 9, a TEM image of the quantum dot obtained in this example shows that the obtained quantum dot has a uniform size and a uniform distribution.
Example 3
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 30 minutes and then carrying out magnetic stirring for 1 hour;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 200 ℃ for 24 hours, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at a heating rate of 15 ℃ per minute to 520 ℃ for 4 hours, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing into 50mL of N-methylpyrrolidone, and carrying out ultrasonic treatment by using a cell disruptor, wherein the ultrasonic disruption power is 700W, the ultrasonic disruption time is 40 minutes, and the ultrasonic disruption temperature is 0 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 80 deg.C for 24 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
Referring to fig. 10, a TEM image of the quantum dot obtained in this example shows that the obtained quantum dot has a uniform size and a uniform distribution.
Example 4
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 30 minutes and then carrying out magnetic stirring for 1 hour;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 200 ℃ for 24 hours, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air, and heating to 520 ℃ at a heating rate of 15 ℃ per minuteKeeping the temperature at the temperature of 4 hours, and then naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing in 50ml of isopropanol, and carrying out ultrasonic treatment by using a cell crusher, wherein the ultrasonic crushing power is 700W, the ultrasonic crushing time is 40 minutes, and the ultrasonic crushing temperature is 0 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 80 deg.C for 24 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
Fig. 11 is a TEM image of the quantum dots obtained in this example, and the obtained quantum dots have uniform size and uniform distribution.
Example 5
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 20 minutes and then carrying out magnetic stirring for 1 hour;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 160 ℃ for 18h, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at a heating rate of 20 ℃ per minute to 500 ℃ for 5 hours, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing in 50ml deionized water, and ultrasonic treating with cell disruptorAnd (3) treating, wherein the ultrasonic crushing power is 1000W, the ultrasonic crushing time is 20 minutes, and the ultrasonic crushing temperature is 10 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 60 deg.C for 24 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
Example 6
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40mL of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 40min and then carrying out magnetic stirring for 40 min;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 200 ℃ for 20 hours, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at a heating rate of 10 ℃ per minute to 600 ℃ for 1 hour, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing into 50ml of absolute ethyl alcohol, and carrying out ultrasonic treatment by using a cell crusher, wherein the ultrasonic crushing power is 500W, the ultrasonic crushing time is 50min, and the ultrasonic crushing temperature is 5 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Then centrifuged at 8000rmp for 5 minutes to give a pale yellow solid at 70 deg.CThen vacuum drying is carried out for 20h to obtain light yellow powder g-C3N4And (4) quantum dots.
Example 7
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, performing ultrasonic treatment for 50 minutes, and then performing magnetic stirring for 50 minutes;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 190 ℃ for 22h, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at the heating rate of 12 ℃ per minute to 580 ℃ for 2 hours, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing in 50ml of isopropanol, and carrying out ultrasonic treatment by using a cell crusher, wherein the ultrasonic crushing power is 10W, the ultrasonic crushing time is 60 minutes, and the ultrasonic crushing temperature is 3 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 90 deg.C for 15 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
Example 8
g-C3N4The preparation method of the quantum dot comprises the following steps:
1. 3g of urea is weighed and dissolved in 40ml of deionized water to be stirred to obtain colorless clear solution
2. Weighing 3g of melamine, adding the melamine into the urea solution obtained in the step 1, and carrying out ultrasonic stirring for 60 minutes and then carrying out magnetic stirring for 1 hour;
3. and (3) transferring the precursor solution obtained in the step (2) into a reaction kettle with a 50ml polytetrafluoroethylene lining, preserving the heat at 170 ℃ for 21h, naturally cooling to room temperature, washing with deionized water and ethanol for multiple times, and drying to obtain a white rod-shaped and layered melamine precursor.
4. Transferring the precursor obtained in the step 3 into a crucible with a cover, wrapping the precursor with an aluminum foil, putting the wrapped precursor into a muffle furnace, calcining the wrapped precursor in air at the heating rate of 18 ℃ per minute to 570 ℃ for 3 hours, and naturally cooling to obtain yellow powdery g-C3N4。
5. 0.5g of the yellow powder g-C obtained in step 43N4Dispersing in 50ml of isopropanol, and carrying out ultrasonic treatment by using a cell crusher, wherein the ultrasonic crushing power is 1800W, the ultrasonic crushing time is 10 minutes, and the ultrasonic crushing temperature is 8 ℃.
6. The yellow solution obtained after ultrasonication was centrifuged at 500rmp for 3 minutes to remove large particles and obtain a pale yellow suspension. The pale yellow suspension was centrifuged at 1500rmp for 3min to remove the next large piece of particles. Centrifuging at 8000rmp for 5min to obtain light yellow solid, vacuum drying at 100 deg.C for 12 hr to obtain light yellow powder g-C3N4And (4) quantum dots.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. g-C3N4The preparation method of the quantum dot is characterized by comprising the following steps:
step 1, dissolving urea in deionized water to obtain a precursor solution;
step 2, adding melamine into the precursor solution, mixing, performing ultrasonic treatment, and performing magnetic stirring after ultrasonic treatment to obtain melamine dispersion liquid;
step 3, carrying out hydrothermal reaction on the melamine dispersion liquid to obtain a reaction system;
step 4, washing the reaction system by water and ethanol, and then separating and purifying to obtain melamine precursor powder; the microstructure of the melamine precursor powder is rod-shaped and lamellar;
step 5, putting the melamine precursor powder into a porcelain boat or an alumina crucible, wrapping the porcelain boat or the alumina crucible with an aluminum foil, calcining in an air environment, and calcining to obtain g-C3N4A bulk material; g to C3N4Dispersing the block material in a solvent, and performing ultrasonic crushing by a cell crushing instrument to obtain yellow turbid liquid;
step 6, purifying the yellow suspension by centrifugal separation, and drying the centrifugal product in vacuum to obtain g-C3N4And (4) quantum dots.
2. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 2, the mass ratio of melamine to urea is 1: 1.
3. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 2, the ultrasonic treatment time is 20-60min, and the magnetic stirring time is more than 30 min.
4. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 3, the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 18-24 h.
5. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 5, the calcination temperature is 500-600 ℃, the heating rate is 10-20 ℃/min, the heat preservation time is 1-5h, and the temperature is naturally reduced after heat preservation.
6. A g-C according to claim 13N4The preparation method of the quantum dot is characterized in that in the step 5, the solvent is deionized water, absolute ethyl alcohol, N-dimethylformamide, N-methylpyrrolidone or isopropanol.
7. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 5, the power of the cell crusher during ultrasonic crushing is 10-1800W, the crushing time is 10-60 min, and the crushing temperature is 0-10 ℃.
8. A g-C according to claim 13N4The preparation method of the quantum dots is characterized in that in the step 6, the vacuum drying temperature is 60-100 ℃, and the vacuum drying time is 12-24 h.
9. g-C obtained by the process of any one of claims 1 to 83N4Quantum dots characterized by g-C3N4The quantum dots are in a wafer shape, and the particle size is 5-15 nm.
10. g-C according to claim 93N4Quantum dot, characterized in that said g-C3N4The quantum dots have the strongest fluorescence emission at 430nm under the excitation of 325nm light.
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| CN110841670A (en) * | 2019-11-21 | 2020-02-28 | 湖南大学 | Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof |
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| CN105670620A (en) * | 2016-03-14 | 2016-06-15 | 山东农业大学 | Preparation method of doped carbon nitride fluorescent quantum dots |
| CN110841670A (en) * | 2019-11-21 | 2020-02-28 | 湖南大学 | Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof |
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