CN113086973A - Method for preparing graphene quantum dots by taking citric acid as raw material - Google Patents
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- CN113086973A CN113086973A CN202110293234.XA CN202110293234A CN113086973A CN 113086973 A CN113086973 A CN 113086973A CN 202110293234 A CN202110293234 A CN 202110293234A CN 113086973 A CN113086973 A CN 113086973A
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000502 dialysis Methods 0.000 claims abstract 3
- 239000006185 dispersion Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000002059 diagnostic imaging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing graphene quantum dots by taking citric acid as a raw material. Firstly, citric acid is taken as a carbon source, a certain amount of citric acid is uniformly dispersed in ionic liquid, a proper amount of deionized water is added into a mixed solution for ultrasonic dispersion, then the mixed solution is transferred into a reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is heated in a drying oven, the mixed solution after the reaction is poured out, and the required graphene quantum dots can be obtained through centrifugation and dialysis treatment. The influence of factors such as the proportion of reaction raw materials and the reaction time on the performance of the graphene quantum dots is researched. The method is simple to operate and easy to popularize and apply on a large scale, and the prepared graphene quantum dots are uniform in size, good in water solubility and stable in fluorescence property.
Description
Technical Field
The invention belongs to the technical field of novel graphene materials, and relates to a method for preparing graphene quantum dots by taking citric acid as a raw material.
Background
The graphene quantum dots are carbon-based zero-dimensional materials. Compared with traditional fluorescent materials such as organic fluorescent dye, semiconductor quantum dots and rare earth fluorescent nanoparticles, the graphene quantum dots have a plurality of excellent performances such as good water solubility, biocompatibility, low toxicity, low cost, environmental friendliness, wide raw material sources and the like. The graphene quantum dots are generally synthesized by a laser ablation method, a chemical oxidation method, a combustion method, an electrochemical synthesis method, an arc discharge method, a hydrothermal synthesis method, a microwave synthesis method and other preparation processes. Due to the excellent performance and the simple preparation method, the graphene quantum dots have good application prospects in various fields such as medical imaging technology, biological detection and sensors, environmental monitoring, chemical analysis, catalysis, energy development and the like.
In 2004, Xu et al reported a method for preparing single-walled carbon nanotubes (SWCNTs) using arc discharge, and discovered for the first time graphene quantum dots that can emit bright fluorescence during the process of purifying the product by electrophoresis. Zhu et al prepare graphene quantum by taking graphite oxide as a raw material and a hydrothermal method. Shen et al developed graphene quanta with surfaces passivated by polyethylene glycol, and observed up-conversion fluorescence imaging under a 808nm fluorescence microscope. Testsuka et al reported a simple chemical process for the preparation of GQDs rich in amino groups on their surface.
With the more intensive research on graphene quantum dots, people make great progress on the synthesis, performance and application aspects of the graphene quantum dots. Meanwhile, the graphene quantum dots are wide in raw material source and low in preparation cost, have great advantages in the field of material preparation, and have good application prospects in wide fields of medical imaging equipment, tiny light-emitting diodes, chemical sensors, photocatalytic reactions and the like. But its greatest limitation is the low autofluorescence quantum yield (< 10%). In addition, an effective functional modification and fluorescence regulation mode is lacked, the light-emitting mechanism is still unclear so far, and the factors limit the development of the graphene quantum dots to different degrees. Therefore, how to obtain graphene quantum dots with high quality, high fluorescence efficiency and adjustable fluorescence, and simultaneously reveal the fluorescence emission mechanism thereof, remains an important and urgent subject for the scientists of chemistry and materials.
According to the method, citric acid is used as a carbon source, and the graphene quantum dots are prepared by a hydrothermal method, so that the method has the advantages of low cost, convenience in operation, simple equipment used, easiness in industrial production and the like. The influence of factors such as raw material ratio and heating time on various performances of the graphene quantum dots is intensively researched. The graphene quantum dots prepared by the method have uniform size, good water solubility and stable fluorescence property, and a simple method is provided for preparing high-quality graphene quantum dots by taking citric acid as a raw material.
Disclosure of Invention
The invention aims to provide a method for preparing graphene quantum dots by taking citric acid as a raw material.
The method comprises the following specific steps:
(1) 0.768g of citric acid solution is uniformly dispersed in 0-26.388g of ionic liquid.
(2) And (2) adding 10ml of deionized water into the dispersion liquid obtained in the step (1), carrying out ultrasonic treatment for 15-30min, and transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining.
(3) And (3) placing the reaction kettle in an oven, and reacting for 3-24 h at 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging and dialyzing at 9000-12000rpm to obtain the graphene quantum dots.
The method is simple to operate, and the prepared graphene quantum dots are uniform in size, good in water solubility and stable in fluorescence property.
Drawings
Fig. 1 is a graph of the ultraviolet-visible absorption spectrum of the graphene quantum dot prepared in example 2.
Fig. 2 is a fluorescence spectrum of the graphene quantum dot prepared in example 2 under different excitation wavelengths.
Detailed Description
Example 1:
(1) 0.768g of citric acid is uniformly dispersed in 10ml of deionized water, and the mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining after being subjected to ultrasonic dispersion for 15 min.
(2) The reaction kettle is placed in an oven and reacts for 12 hours at the temperature of 110 ℃.
(3) Pouring out the mixed solution after the reaction in the step (2), and centrifuging and dialyzing at 9000rpm to obtain the graphene quantum dots.
Example 2:
(1) 0.768g of citric acid was homogeneously dispersed in 0.8796g of ionic liquid.
(2) And (2) adding 10ml of deionized water into the dispersion liquid obtained in the step (1), carrying out ultrasonic dispersion for 15min, and transferring to a reaction kettle with a polytetrafluoroethylene lining.
(3) The reaction kettle is placed in an oven and reacts for 12 hours at the temperature of 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging and dialyzing at 9000rpm to obtain the graphene quantum dots.
Example 3:
(1) 0.768g of citric acid was homogeneously dispersed in 8.796g of ionic liquid.
(2) And (2) adding 10ml of deionized water into the dispersion liquid obtained in the step (1), carrying out ultrasonic dispersion for 15min, and transferring to a reaction kettle with a polytetrafluoroethylene lining.
(3) The reaction kettle is placed in an oven and reacts for 12 hours at the temperature of 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging and dialyzing at 9000rpm to obtain the graphene quantum dots.
Example 4:
(1) 0.768g of citric acid was uniformly dispersed in 26.388g of ionic liquid.
(2) And (2) adding 10ml of deionized water into the dispersion liquid obtained in the step (1), carrying out ultrasonic dispersion for 15min, and transferring to a reaction kettle with a polytetrafluoroethylene lining.
(3) The reaction kettle is placed in an oven and reacts for 12 hours at the temperature of 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging and dialyzing at 9000rpm to obtain the graphene quantum dots.
Example 5:
(1) 0.8796g of ionic liquid is dispersed in 10ml of deionized water, and the mixture is transferred to a reaction kettle with a polytetrafluoroethylene lining after being subjected to ultrasonic treatment for 15 min.
(2) The reaction kettle is placed in an oven and reacts for 12 hours at the temperature of 110 ℃.
(3) Pouring out the mixed liquid after the reaction in the step (2), centrifuging at 9000rpm, and dialyzing to obtain the graphene quantum dots.
Example 6:
(1) 0.768g of citric acid was homogeneously dispersed in 8.796g of ionic liquid.
(2) And (2) ultrasonically dispersing the dispersion liquid obtained in the step (1) for 15min, and then transferring the dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining.
(3) The reaction kettle is placed in an oven and reacts for 3 hours at the temperature of 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging at 9000rpm, dialyzing and filtering to obtain the graphene quantum dots.
Example 7:
(1) 0.768g of citric acid was homogeneously dispersed in 8.796g of ionic liquid.
(2) And (2) ultrasonically dispersing the dispersion liquid obtained in the step (1) for 15min, and then transferring the dispersion liquid into a reaction kettle with a polytetrafluoroethylene lining.
(3) The reaction kettle is placed in an oven and reacts for 24 hours at the temperature of 110 ℃.
(4) Pouring out the mixed solution after the reaction in the step (3), and centrifuging at 9000rpm, dialyzing and filtering to obtain the graphene quantum dots.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471214A (en) * | 2022-02-11 | 2022-05-13 | 中国矿业大学 | A kind of preparation method of glycerol graphene quantum dot nanofluid and nanofluid |
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| EP3085665A1 (en) * | 2014-01-17 | 2016-10-26 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Large-scale preparation method for graphene quantum dots |
| CN107500274A (en) * | 2017-10-11 | 2017-12-22 | 江苏安纳泰环保科技有限公司 | A kind of preparation method of the graphene quantum dot of three primary colors fluorescence |
| CN108529601A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院福建物质结构研究所 | A kind of preparation method of high-quality nitrogen-doped graphene quantum dot |
| CN108892127A (en) * | 2018-07-25 | 2018-11-27 | 重庆交通大学 | A kind of preparation method of amino functional graphene quantum dot |
| CN111073221A (en) * | 2020-01-10 | 2020-04-28 | 中国科学院兰州化学物理研究所 | Preparation method of graphene quantum dot-nanoparticle-epoxy resin composite material |
| CN111690404A (en) * | 2020-05-18 | 2020-09-22 | 中国石油大学(北京) | Fluorescent carbon dot, preparation method thereof and application thereof in detection of p-aminoazobenzene |
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2021
- 2021-03-18 CN CN202110293234.XA patent/CN113086973A/en active Pending
Patent Citations (6)
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| EP3085665A1 (en) * | 2014-01-17 | 2016-10-26 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Large-scale preparation method for graphene quantum dots |
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| CN107500274A (en) * | 2017-10-11 | 2017-12-22 | 江苏安纳泰环保科技有限公司 | A kind of preparation method of the graphene quantum dot of three primary colors fluorescence |
| CN108892127A (en) * | 2018-07-25 | 2018-11-27 | 重庆交通大学 | A kind of preparation method of amino functional graphene quantum dot |
| CN111073221A (en) * | 2020-01-10 | 2020-04-28 | 中国科学院兰州化学物理研究所 | Preparation method of graphene quantum dot-nanoparticle-epoxy resin composite material |
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Non-Patent Citations (4)
| Title |
|---|
| SANG,S: "Hydrothermal synthesis of carbon nano-onions from citric acid", 《CHEMISTRY-AN ASIAN JOURNAL》 * |
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| CN114471214A (en) * | 2022-02-11 | 2022-05-13 | 中国矿业大学 | A kind of preparation method of glycerol graphene quantum dot nanofluid and nanofluid |
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Application publication date: 20210709 |