CN110467916A - Carbon quantum dot green fluorescent material of N doping and preparation method thereof - Google Patents
Carbon quantum dot green fluorescent material of N doping and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to carbon quantum dot green fluorescent materials of a kind of N doping and preparation method thereof.The particle size range of the carbon quantum dot green fluorescent material of the N doping is 3~5 nm.The carbon quantum of this N doping can launch bright green fluorescence under the light excitation of the nm of 270 nm ~ 462, and fluorescence quantum efficiency reaches as high as 55%, and particle size range is 3 ~ 5 nm.This preparation method is using isopropanol as carbon source, using pink salt as catalyst, greatly shortens the generated time for the carbon quantum dot for synthesizing N doping, the fluorescence efficiency of the carbon quantum dot of the N doping of synthesis in 2 hours reaches 36%.The fluorescence property of the carbon quantum dot of the N doping of this method preparation keeps stablizing in the range of pH4 ~ 9.This preparation method greatly simplifies the technique for the carbon quantum dot for synthesizing N doping, improves preparation efficiency, greatly reduces preparation cost.
Description
Technical field
Present invention relates particularly to carbon quantum dot green fluorescent materials of a kind of N doping and preparation method thereof.
Background technique
Carbon quantum dot is the spherical nano material that a kind of partial size is less than 10nm.Carbon quantum dot is in addition to having traditional quantum
Point luminescent properties and small size property outside, also have good water solubility, stable luminescent property, with biomolecule compatibility it is good, at
This low advantage, it is wide that this has it in fields such as bio-imaging, biomedical mulecular luminescence label, mulecular luminescence sensors
Application prospect.
The method of synthesis carbon quantum dot has very much, such as hydro-thermal method, microwave method etc..However, the carbon quantum dot reported at present
The synthetic method General reactions time it is longer, quantum efficiency is not high.Document report is using phenylenediamine as the carbon amounts of nitrogen source hydrothermal synthesis
Sub-, generated time is 12 hours, and the quantum efficiency of green light carbon quantum dot is 17.6%(Kai Jiang, Shan Sun, Ling
Zhang, et al. Angew. Chem. Int. Ed. 2015,54,5360-5363.).Doping element sulphur can be improved
The quantum luminous efficiency of carbon quantum dot, document report adulterates the quantum efficiency of the green light carbon quantum dot of sulphur up to 60%, but this method
Need to react 3 days or more (Xin Wang, Li Cao, Sheng-Tao Yang, et al. Angew. in a nitrogen atmosphere
Chem. Int. Ed. 2010, 49: 5310-5314.).Since the compound molecule majority of sulfur-bearing has niff,
It is unfavorable to human health.Therefore, the luminous material of the carbon quantum dot environmentally protective, generated time is short, at low cost, quantum efficiency is high is found
The novel processing step of material has important research significance and practical value to the extensive and practical application of carbon quantum dot.
Summary of the invention
One of the objects of the present invention is to provide a kind of carbon quantum dot green fluorescent materials of N doping.
The second object of the present invention is to provide the preparation method of the carbon quantum dot green fluorescent material of the N doping.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of carbon quantum dot green fluorescent material of N doping, it is characterised in that the carbon quantum dot green fluorescent material of the N doping
Particle size range be 3~5 nm.
A method of preparing the carbon quantum dot green fluorescent material of above-mentioned N doping, it is characterised in that by m-phenylene diamine (MPD)
It is mixed with isopropanol by the molar ratio of 1:200~1:500, stirs to being completely dissolved, add the pink salt of catalytic amount；150
~180oC is reacted 2~8 hours, is cooled to room temperature, and centrifuge separation removal tin oxide is to obtain the carbon quantum dot green of N doping
Fluorescent material.
Above-mentioned pink salt are as follows: SnCl4·5H2O、SnCl4、SnCl2·2H2O、SnCl2Or SnF2。
The carbon quantum dot of the N doping can be under the light excitation that wavelength is 270 ~ 462 nm, maximum luminous wavelength position
In 500 nm, half-peak breadth is about the emission peak of 75 nm.
The present invention is using isopropanol as carbon source, and m-phenylene diamine (MPD) is nitrogen source, and metal tin compound is catalyst, by carbon quantum
Nitrogen-atoms is adulterated in point, makes emission wavelength red shift to green emitting area, and improve the luminous efficiency of carbon quantum dot.With metallic tin
Conjunction object is catalyst, greatly shortens the generated time of synthesis carbon quantum dot, substantially reduces the synthesis cost of carbon quantum dot；Used
Generated time shortens 50% or more than the time reported in the literature, the quantum efficiency of the green light carbon quantum dot of synthesis in 2 hours up to 36%,
Highest quantum efficiency is up to 55%.The synthetic method carries out in air, does not need complicated synthesis device, does not need chromatography point
From.The synthetic method has high-efficient, the at low cost advantage of synthesis.
The instrument and equipment that the method for the present invention uses is simple, carries out in air atmosphere, does not need chromatographic isolation, synthetic method
Simply, generated time greatly shortens, and shortens 50% or more than the time used in synthetic method reported in the literature, synthesis cost is low.No
It is a kind of environmentally protective synthetic method using sulfur-bearing chemical reagent.
It can be placed half a year or more in the air of the carbon quantum dot for the N doping that the present invention synthesizes at room temperature, luminescent properties are not
Weaken, under the light excitation of the nm of 270 nm ~ 462, issues bright green fluorescence.The nitrogen-doped carbon quantum dot is in room temperature item
Luminescent properties under part have good stability.
Nitrogen-doped carbon quantum dot prepared by the present invention luminescent properties in the buffer solution of pH4 ~ pH9 keep stablizing.
Detailed description of the invention
Fig. 1 is fluorescence emission spectrum of the one gained green light carbon quantum dot of embodiment under 462 nm excitation.
Fig. 2 is fluorescence excitation spectrum of the one gained green light carbon quantum dot of embodiment under 500 nm detection.
Fig. 3 is the uv-visible absorption spectra of one gained green light carbon quantum dot of embodiment.
Fig. 4 is the high-resolution-ration transmission electric-lens figure (HRTEM) of one gained green light carbon quantum dot of embodiment.
Fig. 5 is the infrared spectrogram of one gained green light carbon quantum dot of embodiment.
Fig. 6 is fluorescence spectra of the one gained green light carbon quantum dot of embodiment under different excitation wavelengths.
Fig. 7 is fluorescence emission spectrum of the green light carbon quantum dot under 454 nm excitation in different pH value buffered aqueous solutions.
Specific embodiment
Embodiment one: the reaction time is the green light carbon quantum dot of preparation in 2 hours.
By a certain amount of SnCl4·5H2O is dissolved in the aqueous isopropanol of 10 ~ 15 mL, by a certain amount of m-phenylene diamine (MPD)
It is dissolved in the isopropanol of 10 ~ 20 mL, is transferred in ptfe autoclave after two kinds of solution are mixed, 180oC
Cooled to room temperature after reaction 2 hours.Centrifuge separation obtains the green light carbon quantum dot of High Efficiency Luminescence.
Fig. 1 is the emission spectrum of the carbon quantum dot under the excitation of 462 nm light, and maximum emission wavelength is located at 500 nm.Figure
It is the fluorescence excitation spectrum for monitoring the carbon quantum dot under wavelength that 2, which be with 500 nm, and maximum excitation wavelength is located at 462 nm.Fig. 3 is
The uv-visible absorption spectra of the carbon quantum dot shows that it is main there are three absorption peak, be located at 254 nm, 293 nm and
At 462 nm.Fig. 4 is the high resolution electron microscopy figure (HRTEM) of the carbon quantum dot, shows that the particle size range of the carbon quantum dot is 3 ~ 5
nm.Fig. 5 is the infrared absorption spectrum of the carbon quantum dot, in 3658 cm-1With 3645 cm-1There are two very narrow moderate strengths at place
Absorption peak, be typical-NH2The symmetrical and asymmetric stretching vibration absworption peak of the N-H of group is located at 1382 cm-1Place
The stretching vibration of the C-N on aromatic rings is belonged to compared with strong absworption peak.Show that there is-NH on the surface of the carbon quantum dot2Group.The carbon
Its absolute quantum efficiency of quantum dot stable state transient state Fluorescence Spectrometer FLS1000 test is 36.32%.Fig. 6 is embodiment one
Fluorescence emission spectrum of the carbon quantum dot of middle synthesis under different excitation wavelengths.Show the carbon quantum dot in 270 nm ~ 462
Under the light excitation of nm, capable of emitting bright green fluorescence, maximum luminous wavelength is slightly moved.Fig. 7 is respectively in pH=4,7,9
Fluorescence emission spectrum of the carbon quantum dot under 454 nm excitation in buffer solution.Show that pH value is strong to the fluorescence of the carbon quantum dot
Degree influences less, to illustrate that the carbon quantum dot can be applied in the range of pH=4 ~ 9.
Embodiment two: the reaction time is respectively the green light carbon quantum dot of preparation in 2,4,6,8 hours.
By a certain amount of SnF2It is dissolved in the aqueous isopropanol of 10 ~ 15 mL, a certain amount of m-phenylene diamine (MPD) is dissolved in
In the isopropanol of 10 ~ 20 mL, it is transferred in ptfe autoclave after two kinds of solution are mixed, 180oC difference is anti-
Cooled to room temperature after answering 2,4,6,8 hours.The green light carbon quantum dot of differential responses time preparation can be obtained in centrifuge separation.
The fluorescence quantum efficiency of the green light carbon quantum dot of reaction 2,4,6,8 hours is respectively 36.3%, 55.8%, 49.7%, 48.2%(table
1).
The quantum efficiency of 1 different time of table synthesis carbon quantum dot
| Carbon quantum dot | 2 hours | 4 hours | 6 hours | 8 hours |
| Fluorescence quantum efficiency | 36.3% | 55.8% | 49.7% | 48.2% |
Claims (3)
1. a kind of green light carbon quantum dot of N doping, it is characterised in that the particle size range of the carbon quantum dot of this N doping be 3 ~
5 nm。
2. a kind of preparation method of the carbon quantum dot green fluorescent material of N doping according to claim 1, feature exist
In the specific steps of this method are as follows: mix m-phenylene diamine (MPD) and isopropanol by the molar ratio of 1:200~1:500, stir to complete
Fully dissolved adds the pink salt of catalytic amount；150~180oC is reacted 2~8 hours, is cooled to room temperature, centrifuge separation removal
Tin oxide obtains the carbon quantum dot green fluorescent material of N doping.
3. preparation method according to claim 2, it is characterised in that the pink salt are as follows: SnCl4·5H2O、SnCl4、
SnCl2·2H2O、SnCl2Or SnF2。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112391163A (en) * | 2020-09-30 | 2021-02-23 | 上海大学 | Nitrogen-doped yellow carbon quantum dot and preparation method thereof |
| CN112940720A (en) * | 2021-02-01 | 2021-06-11 | 郑州大学 | Nitrogen-doped carbon nanodot with high luminous efficiency and preparation method thereof |
| CN113089015A (en) * | 2021-03-29 | 2021-07-09 | 西北大学 | Nitrogen-doped carbon quantum dot and preparation method thereof, reduced graphene oxide and preparation method and application thereof |
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| CN104710983A (en) * | 2015-03-02 | 2015-06-17 | 四川大学 | Method for preparing nitrogen-doped graphene quantum dots through metal ion coordination catalysis |
| CN105295909A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for using phenylenediamine and citric acid for preparing carbon quantum dot marking probe for cell developing |
| CN105713608A (en) * | 2016-01-27 | 2016-06-29 | 太原理工大学 | Preparation method of size-controllable nitrogen-doped carbon quantum dots |
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Patent Citations (3)
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| CN104710983A (en) * | 2015-03-02 | 2015-06-17 | 四川大学 | Method for preparing nitrogen-doped graphene quantum dots through metal ion coordination catalysis |
| CN105295909A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for using phenylenediamine and citric acid for preparing carbon quantum dot marking probe for cell developing |
| CN105713608A (en) * | 2016-01-27 | 2016-06-29 | 太原理工大学 | Preparation method of size-controllable nitrogen-doped carbon quantum dots |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112391163A (en) * | 2020-09-30 | 2021-02-23 | 上海大学 | Nitrogen-doped yellow carbon quantum dot and preparation method thereof |
| CN112391163B (en) * | 2020-09-30 | 2022-11-18 | 上海大学 | Nitrogen-doped yellow carbon quantum dot and preparation method thereof |
| CN112940720A (en) * | 2021-02-01 | 2021-06-11 | 郑州大学 | Nitrogen-doped carbon nanodot with high luminous efficiency and preparation method thereof |
| CN113089015A (en) * | 2021-03-29 | 2021-07-09 | 西北大学 | Nitrogen-doped carbon quantum dot and preparation method thereof, reduced graphene oxide and preparation method and application thereof |
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