CN115011339A - Graphene quantum dot and preparation method thereof - Google Patents
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Abstract
The invention discloses a graphene quantum dot and a preparation method thereof, wherein Congo red is used as a raw material, and the graphene quantum dot emitting blue-violet fluorescence is obtained through thermocatalytic synthesis of activated alumina at 300-600 ℃.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a graphene quantum dot and a preparation method thereof.
Background
The graphene quantum dots are discovered in 2009 to be zero-dimensional nano materials, the size of the graphene quantum dots is 1-20 nanometers, and the graphene quantum dots have great application prospects in the fields of biomedicine, display screens, biosensing, electrochemical sensing, environmental monitoring, new energy, electronic devices, composite materials, lasers and the like, the key difficulty of the graphene quantum dot industrialization at present is that the graphene quantum dots cannot be prepared in a large scale, just as the peng cheng teaching of the university of southern science of singapore is published on the advanced academic journal, an paper, a large amount of application of the graphene quantum dots at present cannot be realized, and a method for synthesizing the graphene quantum dots in a large scale and at low cost cannot be realized (adv. mater.2019,31,1808283). Due to the defects of the existing preparation method, for example, graphene is used as a raw material, and the like, the graphene quantum dots cannot be industrialized on a global scale. One of the application fields of the graphene quantum dots is biological imaging, the market of the biological imaging field is huge, and the existing biological imaging materials mainly comprise organic micromolecule fluorescent dyes, semiconductor quantum dots, nanogold and graphene quantum dots. Wherein, the organic micromolecule fluorescent dye has poor chemical stability and the photobleaching problem; the semiconductor quantum dots have high toxicity or are difficult to be used in an aqueous solution system, and the price of the nano gold is high; the graphene quantum dots are low in cytotoxicity, soluble in water and ideal biological imaging materials. The second application field of the graphene quantum dots is a biosensor, and the biosensor is a detection instrument for detecting biological substances, is an instrument for converting the concentration of the biological substances into an electric signal, and is widely applied to the medical field. The third application field of the graphene quantum dots is immunochromatography detection, the immunochromatography detection technology is an analysis method combining an immunological technology and a chromatographic technology, and the immunochromatography detection technology is widely applied to the fields of clinical diagnosis, environmental monitoring and food safety, the conventional immunochromatography technology uses nanogold, the price is high, the detection accuracy is not high, and the graphene quantum dots can replace the nanogold to be used for immunochromatography detection. The fourth application field of the graphene quantum dots is cancer diagnosis and treatment, and in the aspect of cancer diagnosis, as the folic acid content on the surface of a cancer cell is obviously higher than that of other cells, the graphene quantum dots are loaded with specific folic acid molecules to realize visual diagnosis of the cancer cell, which is detailed in adv. In the aspect of cancer drug delivery and treatment, due to the fact that a large number of groups are arranged on the surface of the graphene quantum dot layered structure, the drug loading capacity is large, and the drug effect of chemotherapeutic drugs such as the adriamycin can be greatly improved. See adv.mater.2019,1904364 for details, in addition, graphene quantum dots can also be used in new methods for treating cancers such as photothermal therapy and photodynamic therapy. The photothermal therapy is to combine the graphene quantum dots with a near-infrared photothermal agent and perform photothermal conversion to treat cancer. Photodynamic therapy is the release of atomic oxygen through graphene quantum dots to kill cancer cells. The fifth application field of the graphene quantum dots is QLED quantum dot display, and the trend of the QLED to surpass the OLED is realized by the display technology which is updated compared with the OLED by the QLED from the conflict of rear projection, the conflict of plasma and liquid crystal and the conflict of QLED and OLED at present under the promotion of television huge heads such as Samsung, TCL, Hisense and Philips. The quantum dots used for the quantum dot television at present are semiconductor quantum dots, are water-repellent, toxic due to heavy metal cadmium and high in cost, and have obvious advantages and huge market potential once the graphene quantum dots are industrialized.
Disclosure of Invention
The invention aims to disclose a graphene quantum dot and a preparation method thereof, and aims to solve the problems that the preparation method of the graphene quantum dot in the prior art is low in efficiency, usually requires dozens of hours, is complex in product, difficult to separate, uneven in size, low in quantum yield and the like. In order to achieve the purpose, the invention adopts the following preparation method:
step one, preparing a Congo red aqueous solution: dissolving Congo red in deionized water to obtain a Congo red aqueous solution;
step two, preparation of activated alumina: carrying out flash combustion on aluminum hydroxide to obtain activated aluminum oxide;
step three, preparing a mixture: adding a certain amount of active alumina into the Congo red aqueous solution, uniformly mixing, and drying the uniformly mixed sample in a drying oven at 150 ℃ to obtain a mixture;
step four: preparing a graphene quantum dot aqueous solution: placing the mixture in a muffle furnace, carrying out thermocatalytic synthesis in an air atmosphere at 300-600 ℃, and soaking the mixture after thermocatalytic synthesis in water to obtain a leaching solution, namely a graphene quantum dot aqueous solution;
step five: preparing graphene quantum dots: and freeze-drying the graphene quantum dot aqueous solution to obtain the graphene quantum dot.
Wherein the thermal catalytic synthesis temperature is 300-600 ℃, preferably 400-500 ℃, the synthesis time is 30-60 min, and the active aluminum oxide is obtained by flash firing aluminum hydroxide at 400-600 ℃.
The graphene quantum dot prepared by the method has colorless aqueous solution under visible light, has the emission wavelength of 350-490 nm of full-wave-band blue-violet light, shows the property of two-point excitation, has the excitation wavelength of 280nm and 330nm, has excellent high-temperature resistance, has the highest temperature resistance of 630 ℃, and has the absolute quantum yield of more than 80%.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the graphene quantum dots prepared in example 1
FIG. 2 is a high resolution graph of the graphene quantum dots prepared in example 1, with a lattice spacing of 0.21nm
FIG. 3 is a fluorescence spectrum of the graphene quantum dots prepared in example 2
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, still fall within the scope of protection of the present invention.
Example 1
Dissolving 1g of Congo red in 100 g of deionized water to obtain a Congo red aqueous solution, adding 50g of activated alumina powder into the Congo red aqueous solution, uniformly mixing, flashing the activated alumina at 400 ℃ to obtain activated alumina, drying the uniformly mixed sample in a 150 ℃ drying oven, placing the dried sample in a muffle furnace for heat treatment at 300 ℃ in an air atmosphere for 60 minutes, soaking a product obtained after the thermocatalytic synthesis in water to obtain a graphene quantum dot aqueous solution, and freeze-drying the graphene quantum dot aqueous solution to obtain the graphene quantum dot.
Example 2
A method for preparing full-waveband bluish violet fluorescent graphene quantum dots comprises the steps of dissolving 1g of Congo red in 100 g of deionized water to obtain a Congo red aqueous solution, adding 50g of activated alumina powder into the Congo red aqueous solution, uniformly mixing, flashing the activated alumina at 500 ℃ to obtain activated alumina, drying the uniformly mixed sample in a 150 ℃ drying oven, placing the dried sample in a muffle furnace for heat treatment at 400 ℃ in an air atmosphere for 30 minutes, soaking a product obtained after thermal catalysis synthesis in water to obtain a graphene quantum dot aqueous solution, and freeze-drying the graphene quantum dot aqueous solution to obtain the graphene quantum dots. The obtained graphene quantum dot fluorescence 3D scan is as shown in fig. 1, and the absolute quantum yield of the graphene quantum dot is 82%.
Example 3
A method for preparing full-waveband bluish violet fluorescent graphene quantum dots comprises the steps of dissolving 1g of Congo red in 100 g of deionized water to obtain a Congo red aqueous solution, adding 50g of activated alumina powder into the Congo red aqueous solution, uniformly mixing, carrying out flash firing on the activated alumina at 600 ℃, drying the uniformly mixed sample in a 150 ℃ drying oven, carrying out heat treatment on the dried sample in a muffle furnace at 500 ℃ in an air atmosphere for 30 minutes, soaking a product obtained after thermal catalysis synthesis in water to obtain a graphene quantum dot aqueous solution, and carrying out freeze drying on the graphene quantum dot aqueous solution to obtain the graphene quantum dots. The obtained transmission electron microscope image of the graphene quantum dots is shown in the attached figure 2.
Example 4
A method for preparing full-waveband bluish violet fluorescent graphene quantum dots comprises the steps of dissolving 1g of Congo red in 100 g of deionized water to obtain a Congo red aqueous solution, adding 50g of activated alumina powder into the Congo red aqueous solution, uniformly mixing, flashing the activated alumina at 600 ℃ to obtain activated alumina, drying the uniformly mixed sample in a 150 ℃ drying oven, placing the dried sample in a muffle furnace for heat treatment at 600 ℃ in an air atmosphere for 30 minutes, soaking a product obtained after thermal catalysis synthesis in water to obtain a graphene quantum dot aqueous solution, and freeze-drying the graphene quantum dot aqueous solution to obtain the graphene quantum dots.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of graphene quantum dots is characterized by comprising the following steps:
step one, preparing a Congo red aqueous solution: dissolving Congo red in deionized water to obtain a Congo red aqueous solution;
step two, preparation of activated alumina: carrying out flash combustion on aluminum hydroxide to obtain activated aluminum oxide;
step three, preparing a mixture: adding a certain amount of active alumina into the Congo red aqueous solution, uniformly mixing, and drying the uniformly mixed sample in a drying oven at 150 ℃ to obtain a mixture;
step four: preparing a graphene quantum dot aqueous solution: placing the mixture in a muffle furnace, carrying out thermocatalytic synthesis at 300-600 ℃ in air atmosphere for 30-60 min, and soaking the mixture after thermocatalytic synthesis in water to obtain a leaching solution, namely a graphene quantum dot aqueous solution;
step five: preparing graphene quantum dots: and (3) freeze-drying the graphene quantum dot aqueous solution to obtain the graphene quantum dot.
2. The method for preparing the graphene quantum dot according to claim 1, wherein the thermocatalytic synthesis temperature in the third step is 400-500 ℃ and the synthesis time is 30 min.
3. The method for preparing graphene quantum dots according to claim 1, wherein the flash firing temperature of the aluminum hydroxide in the second step is 400 ℃ to 600 ℃.
4. The graphene quantum dot prepared by the preparation method according to any one of claims 1 to 3, wherein the graphene quantum dot aqueous solution is colorless under visible light.
5. The graphene quantum dot prepared by the preparation method according to any one of claims 1 to 3, wherein the emission wavelength of the graphene quantum dot is within the full-wave range of blue-violet light of 350nm to 490 nm.
6. The graphene quantum dot prepared by the preparation method according to any one of claims 1 to 3, wherein the excitation wavelength of the graphene quantum dot is 280nm and 330 nm.
7. The graphene quantum dot prepared by the preparation method according to any one of claims 1 to 3, wherein the graphene quantum dot has a maximum temperature resistance of 630 ℃.
8. The graphene quantum dot prepared by the preparation method according to any one of claims 1 to 3, wherein the absolute quantum yield of the graphene quantum dot is more than 80%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150284318A1 (en) * | 2013-04-25 | 2015-10-08 | University Of North Dakota | Graphene quantum dots and method of making |
| CN108485659A (en) * | 2018-02-12 | 2018-09-04 | 上海大学 | Amphiphilic graphene quantum dot material, preparation method and its application that fluorescence probe is imaged as cell nucleus targeting |
| KR20200050810A (en) * | 2018-11-02 | 2020-05-12 | 그래핀스퀘어 주식회사 | A process for manufacturing graphene quantum dots and graphene quantum dots prepared therefrom |
| WO2021120800A1 (en) * | 2019-12-16 | 2021-06-24 | 华南理工大学 | Lignin-based graphene quantum dot, preparation method therefor and use thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150284318A1 (en) * | 2013-04-25 | 2015-10-08 | University Of North Dakota | Graphene quantum dots and method of making |
| CN108485659A (en) * | 2018-02-12 | 2018-09-04 | 上海大学 | Amphiphilic graphene quantum dot material, preparation method and its application that fluorescence probe is imaged as cell nucleus targeting |
| KR20200050810A (en) * | 2018-11-02 | 2020-05-12 | 그래핀스퀘어 주식회사 | A process for manufacturing graphene quantum dots and graphene quantum dots prepared therefrom |
| WO2021120800A1 (en) * | 2019-12-16 | 2021-06-24 | 华南理工大学 | Lignin-based graphene quantum dot, preparation method therefor and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王婷婷;李莉;安琪;刁娟娟;: "热解柠檬酸法制备石墨烯量子点及其光学性质研究", 新疆医科大学学报, no. 05, pages 96 - 100 * |
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