CN111977640B - Preparation method of green fluorescent graphene quantum dot powder - Google Patents
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- NFEURUSKIHJCRP-UHFFFAOYSA-N 1,2,3-trinitropyrene Chemical compound C1=CC=C2C=CC3=C([N+]([O-])=O)C([N+](=O)[O-])=C([N+]([O-])=O)C4=CC=C1C2=C43 NFEURUSKIHJCRP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of green fluorescent graphene quantum dot powder, which comprises the steps of firstly using thiourea and 1,3, 6-trinitropyrene as raw materials, preparing a graphene quantum dot solution through a hydrothermal reaction, mixing the graphene quantum dot solution with melamine and paraformaldehyde, and preparing the solid green fluorescent graphene quantum dot powder through a one-pot method. According to the invention, the prepolymer is not required to be prepared, the solid graphene quantum dots are directly prepared by a one-pot method, the preparation method is simplified, the preparation time is shortened, and the prepared green fluorescent graphene quantum dot powder has better fluorescent efficiency, so that the green fluorescent graphene quantum dot powder can be used for preparing high-quality LED devices.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of green fluorescent graphene quantum dot powder.
Background
Graphene Quantum Dots (GQDs) are quasi-zero-dimensional nanomaterials, and the movement of electrons in the graphene quantum dots in all directions is limited, so that the quantum confinement effect is particularly remarkable, and the graphene quantum dots have many unique properties. This will bring revolutionary changes to the fields of electronics, optoelectronics, and electromagnetism. Graphene quantum dot based materials may result in lower production costs for LED displays and solar cells. The new GQDs do not use any toxic metals (e.g., cadmium, lead, etc.). The use of GQD-based materials may make future OLED panels lighter, more flexible, and less costly.
The existing methods for synthesizing graphene quantum dots mainly fall into two categories: top-down methods and bottom-up methods. The top-down method comprises the following steps: under extreme conditions, graphene materials, which are cheap and can be used in large quantities, are decomposed or exfoliated into small-sized GQDs by physical or chemical means. Generally, this method requires multiple steps, and requires the use of concentrated acids, strong oxidants, or high temperature and pressure, and lacks precise control of morphology and size distribution of graphene quantum dots. The bottom-up method mainly involves the synthesis of GQDs from polycyclic aromatic compounds or other aromatic molecular structures (such as fullerenes), mainly including solution chemistry, ultrasound, and microwave methods.
When the graphene quantum dots prepared by the method are dispersed in a solution, the fluorescence quantum yield is very high, but the fluorescence quantum yield is sharply reduced in a solid state, and even no light is emitted. This is because in the solid state, graphene quantum dots have strong pi-pi accumulation with each other, which causes dissipation of excited state energy, and finally causes rapid reduction or even complete loss of fluorescence intensity, causing fluorescence Quenching (ACQ). The potential application of graphene quantum dots in optoelectronic devices such as LEDs is greatly limited by the property of the graphene quantum dots. Therefore, it is very important to develop a preparation method of a novel green-emitting graphene quantum dot powder.
Disclosure of Invention
The invention aims to provide a preparation method of green fluorescent graphene quantum dot powder, which is simple in preparation process, can overcome the limitation of application of graphene quantum dots in LED devices in the prior art, and lays a foundation for application of the graphene quantum dots in photoelectric devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of green fluorescent graphene quantum dot powder comprises the following steps:
1) Dissolving thiourea in water, adding 1,3, 6-trinitropyrene, performing ultrasound in a 500W ultrasonic pulverizer to fully mix the solution, and transferring the mixed solution to a polytetrafluoroethylene reaction kettle for hydrothermal reaction;
2) After the hydrothermal reaction, cooling the reaction liquid to room temperature, performing suction filtration by adopting a nylon membrane of 0.22 mu m, and dialyzing by using a dialysis bag of 1000D to 3500D;
3) Dissolving melamine and paraformaldehyde in water, mixing with the graphene quantum dot solution obtained outside the dialysis bag in the step 2), and heating in a water bath under the action of a magnetic stirrer to obtain graphene quantum dot microspheres;
4) And placing the obtained graphene quantum dots in an oven for microsphere drying to obtain the green fluorescent graphene quantum dot powder.
The molar ratio of trinitropyrene to thiourea used in step 1) is 1 to 10 to 1. The ultrasonic time is 0.5 to 2h; the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 8-12h.
The dialysis time in the step 2) is 12 to 24h.
The mass ratio of the melamine to the paraformaldehyde in the step 3) is 1: (1 to 4); the mass-volume ratio of the melamine to the graphene quantum dot solution is 1: (25-100) g/mL, wherein the concentration of the graphene quantum dot solution is 0.1wt%; the temperature of the water bath heating is 85 to 95 ℃, and the time is 0.5 to 2h.
The drying temperature in the step 4) is 70-90 ℃, and the drying time is 8-12h.
The green fluorescent graphene quantum dot powder prepared by the method can be used for preparing LED devices.
According to the invention, the pyrene is used as a precursor, the thiourea with low toxicity is used as a modifier, the green fluorescent graphene quantum dots with good water solubility are hydrothermally synthesized in a water phase in one step, the synthesis process is simple and environment-friendly, and the danger of the synthesis process is reduced. The graphene quantum dot solution is prepared into graphene quantum dot powder, so that the fluorescence quenching effect caused by aggregation of the graphene quantum dot powder is overcome, and the graphene quantum dot solution is more convenient to apply to LED devices.
The patent applied before the subject group, "a preparation method of solid luminescent graphene quantum dots" (CN 111334294A) provides a technology for preparing solid luminescent graphene quantum dots, which requires that melamine and paraformaldehyde are mixed to prepare a prepolymer, and then the prepolymer is mixed with a graphene quantum dot solution to prepare the solid luminescent graphene quantum dots. However, the prepared prepolymer cannot be stored for a long time, and once the storage time exceeds 3 days, the prepolymer will be polymerized to generate precipitates, so that the doping of the graphene quantum dots is difficult to realize. This is not only unfavorable for the stability of product performance, also is not favorable to industrialization volume production.
According to the invention, melamine, paraformaldehyde and the graphene quantum dot solution are directly mixed for polymerization reaction by a one-pot method, so that the graphene quantum dots are dispersed in the polymer microspheres, the agglomeration among the graphene quantum dots can be effectively reduced, the graphene quantum dots can still emit strong fluorescence in a solid state, the step of prepolymer preparation can be omitted, the preparation method is greatly simplified, and the preparation time is shortened. The graphene quantum dot powder prepared by the one-pot method has higher fluorescence quantum yield which is 16.3 percent and is improved by 22 percent compared with the traditional method, the preparation time is shortened by 50 percent, the production efficiency can be obviously improved, and the industrialized mass production is favorably realized.
In a word, the preparation method of the green fluorescent graphene quantum dot powder has the advantages of simplicity in operation, safety, environmental friendliness and the like, can overcome the problems of difficulty in doping, quenching of solid fluorescence and the like of the existing graphene quantum dot, and provides possibility for application of the graphene quantum dot powder in photoelectric devices.
Drawings
Fig. 1 is a fluorescence emission spectrum of the green fluorescent graphene quantum dot solution prepared in example 1 under excitation of 360nm laser.
Fig. 2 is a fluorescence emission spectrum of the green fluorescent graphene quantum dot powder prepared in example 1 under excitation of 360nm laser.
Fig. 3 is a sample diagram of the green fluorescent graphene quantum dot powder prepared in example 1 under a white light and 365nm ultraviolet fluorescent lamp.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Dissolving 4.508g (0.06 mol) of thiourea in 100mL of ultrapure water, adding 0.5g (0.0015 mol) of 1,3, 6-trinitropyrene, then carrying out ultrasonic treatment in a 500W ultrasonic crusher for 120 minutes to fully mix the solution, transferring the mixed solution into a 200mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 10 hours; after the reaction liquid is cooled to room temperature, carrying out suction filtration by using a 0.22 mu m nylon membrane, dialyzing the filtrate for 24 hours by using a 3500D dialysis bag, and adjusting the concentration of the graphene quantum dot solution obtained outside the dialysis bag to 0.1wt% for later use.
Dissolving 0.39g of melamine and 0.56g of paraformaldehyde in 15mL of ultrapure water, then adding 15mL of 0.1wt% graphene quantum dot solution, adjusting the rotating speed of a magnetic stirrer to 250r/min to fully mix the materials, and heating the materials in a water bath at 95 ℃ for 40 minutes; and after cooling, drying the green fluorescent graphene quantum dots in a drying oven at 80 ℃ for 12 hours to obtain green fluorescent graphene quantum dot powder, wherein the fluorescent quantum yield of the green fluorescent graphene quantum dots is 16.3%.
Example 2
Dissolving 4.508g (0.06 mol) of thiourea in 100mL of ultrapure water, adding 0.4g (0.0012 mol) of 1,3, 6-trinitropyrene, then carrying out ultrasonic treatment in a 500W ultrasonic pulverizer for 30 minutes to fully mix the solutions, transferring the mixed solution to a 200mL of polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 10 hours at 190 ℃; and after the reaction liquid is cooled to room temperature, carrying out suction filtration by using a 0.22 mu m nylon membrane, dialyzing the filtrate for 18 hours by using a 3500D dialysis bag, and adjusting the concentration of the graphene quantum dot solution obtained outside the dialysis bag to 0.1wt% for later use.
Dissolving 0.39g of melamine and 0.39g of paraformaldehyde in 15mL of ultrapure water, then adding 15mL of 0.1wt% graphene quantum dot solution, adjusting the rotating speed of a magnetic stirrer to 250r/min to fully mix the materials, and carrying out water bath heating at 85 ℃ for 120 minutes; and after the graphene quantum dots are cooled, drying the graphene quantum dots in a drying oven at 70 ℃ for 12 hours to obtain green fluorescent graphene quantum dot powder, wherein the fluorescent quantum yield of the green fluorescent graphene quantum dot powder is 15.8%.
Example 3
Dissolving 4.508g (0.06 mol) of thiourea in 100mL of ultrapure water, adding 2.0g (0.006 mol) of 1,3, 6-trinitropyrene, then carrying out ultrasonic treatment in a 500W ultrasonic crusher for 60 minutes to fully mix the solution, transferring the mixed solution into a 200mL of polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 12 hours; and after the reaction liquid is cooled to room temperature, carrying out suction filtration by using a 0.22 mu m nylon membrane, dialyzing the filtrate for 12 hours by using a 3500D dialysis bag, and adjusting the concentration of the graphene quantum dot solution obtained outside the dialysis bag to 0.1wt% for later use.
Dissolving 0.39g of melamine and 1.56g of paraformaldehyde in 15mL of ultrapure water, then adding 15mL of 0.1wt% graphene quantum dot solution, adjusting the rotating speed of a magnetic stirrer to 250r/min to fully mix the materials, and heating the materials in a water bath at 90 ℃ for 60 minutes; and after cooling, drying the green fluorescent graphene quantum dots in a drying oven at 90 ℃ for 10 hours to obtain green fluorescent graphene quantum dot powder, wherein the fluorescent quantum yield of the green fluorescent graphene quantum dots is 15.4%.
Comparative example
Dissolving 4.508g (0.06 mol) of thiourea in 100mL of ultrapure water, adding 0.5g (0.0015 mol) of 1,3, 6-trinitropyrene, then carrying out ultrasonic treatment in a 500W ultrasonic pulverizer for 120 minutes to fully mix the solutions, transferring the mixed solution to a 200mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 10 hours at 200 ℃; and after the reaction liquid is cooled to room temperature, carrying out suction filtration by using a 0.22 mu m nylon membrane, dialyzing the filtrate for 24 hours by using a 3500D dialysis bag, and adjusting the concentration of the graphene quantum dot solution obtained outside the dialysis bag to 0.1wt% for later use.
0.39g of melamine and 0.56g of paraformaldehyde were dissolved in 15mL of ultrapure water, and the resulting solution was transferred to a 50 ℃ water bath and heated for 40 minutes with a magnetic stirrer at 250r/min to obtain a transparent prepolymer solution. And (3) taking 15mL of prepolymer solution and 15mL of graphene quantum dot solution, fully and uniformly mixing, and stirring and heating in a 95 ℃ water bath kettle for 40 minutes. And after cooling, drying the green fluorescent graphene quantum dots in a drying oven at 80 ℃ for 12 hours to obtain green fluorescent graphene quantum dot powder, wherein the fluorescent quantum yield of the green fluorescent graphene quantum dots is 13.4%.
Compared with the comparative example, the preparation of the graphene quantum dot powder by the one-pot method in example 1 can save 40 minutes, namely, about 50% of time is saved, and the fluorescence quantum yield is improved by 22% compared with the comparative example.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of green fluorescent graphene quantum dot powder is characterized by comprising the following steps: the method comprises the following steps:
1) Dissolving thiourea in water, adding 1,3, 6-trinitropyrene, performing ultrasonic treatment to fully mix the solution, and performing hydrothermal reaction;
2) After the hydrothermal reaction, cooling the reaction liquid to room temperature, carrying out suction filtration, and then dialyzing by using a dialysis bag;
3) Dissolving melamine and paraformaldehyde in water, mixing with the graphene quantum dot solution obtained outside the dialysis bag in the step 2), and heating in a water bath under magnetic stirring to obtain graphene quantum dot microspheres;
4) And drying the obtained graphene quantum dot microspheres to obtain the green fluorescent graphene quantum dot powder.
2. The preparation method of green fluorescent graphene quantum dot powder according to claim 1, characterized in that: the molar ratio of 1,3, 6-trinitropyrene to thiourea used in the step 1) is 1 to 10 to 1.
3. The method for preparing green fluorescent graphene quantum dot powder according to claim 1, characterized in that: the time of ultrasonic treatment in the step 1) is 0.5 to 2h; the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 8-12h.
4. The method for preparing green fluorescent graphene quantum dot powder according to claim 1, characterized in that: in the step 2), a filter membrane with the diameter of 0.22 mu m is adopted for suction filtration; the molecular weight cut-off of the dialysis bag is 1000D to 3500D; the dialysis time is 12 to 24h.
5. The method for preparing green fluorescent graphene quantum dot powder according to claim 1, characterized in that: the mass ratio of the melamine to the paraformaldehyde in the step 3) is 1: (1 to 4); the mass-volume ratio of the melamine to the graphene quantum dot solution is 1: (25-100) g/mL, wherein the concentration of the graphene quantum dot solution is 0.1wt%.
6. The method for preparing green fluorescent graphene quantum dot powder according to claim 1, characterized in that: the temperature of water bath heating in the step 3) is 85-95 ℃, and the time is 0.5-2h.
7. The preparation method of green fluorescent graphene quantum dot powder according to claim 1, characterized in that: the drying temperature in the step 4) is 70-90 ℃, and the drying time is 8-12h.
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