CN110317606A - Utilize the method and product of bromoacetonitrile and glyoxaline compound preparation carbon dots - Google Patents
Utilize the method and product of bromoacetonitrile and glyoxaline compound preparation carbon dots Download PDFInfo
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- CN110317606A CN110317606A CN201910701856.4A CN201910701856A CN110317606A CN 110317606 A CN110317606 A CN 110317606A CN 201910701856 A CN201910701856 A CN 201910701856A CN 110317606 A CN110317606 A CN 110317606A
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Abstract
The invention discloses the methods and product using bromoacetonitrile and glyoxaline compound preparation carbon dots, specifically mix bromoacetonitrile and 1- methylimidazole, directly react and carbon dots are made.Method synthesis process of the invention is simply green, and synthesized carbon dots have good fluorescence property and photostability, provides new method for the synthesis of carbon dots.
Description
Technical field
The present invention relates to the preparations of nano luminescent material, and in particular to prepares carbon dots using bromoacetonitrile and glyoxaline compound
Method, further relate to utilize product made from this method.
Background technique
Carbon dots are a kind of novel fluorescent nano particles, and since it has much, such as fluorescent stability is good, toxicity is low, raw
The advantages that object compatibility is high, chemical property is stablized, has caused the extensive concern of researcher.With traditional fluorescent material it is all if any
Engine dyeing material is compared with semiconductor-quantum-point, and carbon dots have many merits, such as very strong fluorescence, up-conversion luminescence performance, change
Photobleaching, good biocompatibility, low cost and the hypotoxicity etc. that property is stable, dispersibility in water is very good, low are learned, this
A little excellent properties make its favor by scientist.Therefore, carbon dots have been widely used in many fields, including electrochemistry
Sensing carries many fields such as medicine, photo-thermal and optical dynamic therapy, photocatalysis, energy storage and battery.
The method of synthesis carbon dots can substantially be divided into two major class: top-to-bottom method and bottom-to-top method.From
Carbon material of macromolecular such as carbon nanotube, graphite, carbon dust, graphene etc. is mainly passed through physics or change by the method under above
Method is cut to small nano particle, and most of cutting process is non-selective.Bottom-to-top method is main
It is that carbon dots are finally obtained by certain method using organism as presoma, these methods include pyrolysis/chemical oxidization method/hydro-thermal
The selection face of method, template, microwave or ultrasonic method etc., presoma is very wide.In addition to this, still an alternative is that passing through surface
It is passivated with functionalization and debugs the photoluminescent property of carbon dots.But above-mentioned synthetic method is required to external energy, therefore is badly in need of one kind
Green, the carbon dots synthetic method of low energy consumption.
Summary of the invention
In view of this, preparing carbon dots using bromoacetonitrile and glyoxaline compound one of the objects of the present invention is to provide a kind of
Method；The second object of the present invention is to provide carbon dots prepared by the above method.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, using the method for bromoacetonitrile and glyoxaline compound preparation carbon dots, after bromoacetonitrile is mixed with glyoxaline compound
It directly reacts, carbon dots is made.
Preferably, the glyoxaline compound is at least one of 1- vinyl imidazole or 1- methylimidazole.
Preferably, the bromoacetonitrile is that 1:1~1:3 is mixed with glyoxaline compound by volume.
Preferably, the temperature of the reaction is 5~40 DEG C.
Preferably, the mixing can use existing any hybrid mode, more preferably be mixed using agitating mode.
Preferably, the time of the reaction is at least 1s；It is furthermore preferred that the reaction time is 1s~10min.
It preferably, further include that carbon dots are collected after the reaction, it is specially that reaction solution is cooling, it is centrifuged, filters, dialyse, freeze
Do to obtain carbon dots powder.
Preferably, the centrifugation is in 10~20min of 8000rpm centrifugation；It is described to be filtered into the miillpore filter with 0.22 μm
Filtering；The dialysis is the 24~48h of bag filter dialysis for being 500Da with molecular cut off.
2, carbon dots made from the method are utilized.
Preferably, the average grain diameter is 17.9nm；Particle size distribution range is 12-22nm.
The beneficial effects of the present invention are: the invention discloses the sides using bromoacetonitrile and glyoxaline compound preparation carbon dots
Method, method of the invention can direct stirring to obtain carbon dots at room temperature, synthesis step is simple, and condition is controllable, is not necessarily to energy consumption, green
Color is friendly, and the reaction time is short, produces carbon dots in second grade, searches out new synthetic method, carbon obtained for carbon dots synthesis
Point has many advantages, such as good fluorescence property and water solubility.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Illustrate:
Fig. 1 is the transmission electron microscope figure of the obtained carbon dots of the present invention.
Fig. 2 is the histogram of particle size distribution of the obtained carbon dots of the present invention.
Fig. 3 is the uv absorption spectra of the obtained carbon dots of the present invention.
Fig. 4 is obtained emission spectrum of the carbon dots under different excitation wavelengths of the present invention.
Fig. 5 is the quantum yield data processing figure of quinine sulfate standard sample.
Fig. 6 is the quantum yield data processing figure of the obtained carbon dots of the present invention.
Fig. 7 is the uv absorption spectra that carbon dots are made in embodiment 4.
Fig. 8 is that emission spectrum of the carbon dots under different excitation wavelengths is made in embodiment 4.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It better understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
Utilize the method for bromoacetonitrile and 1- methylimidazole preparation carbon dots, comprising the following steps:
(1) 2mL bromoacetonitrile and 6mL 1- methylimidazole are measured respectively, is poured into 50mL beaker, is stirred rapidly, keep solution mixed
It closes uniformly, stands reaction to get reaction solution, carbon dots are contained in reaction solution；
(2) it by after reaction solution natural cooling obtained by step (1), is centrifuged under 8000rpm speed in supercentrifuge
10min obtains supernatant；Then the filtering with microporous membrane for being 0.22 μm by supernatant filter membrane, filtrate are with molecular cut off again
After the bag filter dialysis 48h of 500Da, freeze-drying obtains carbon dots powder；A part of carbon dots powder is finally taken to use ultrapure water respectively
Disperse with ethyl alcohol, obtains carbon dots dispersion liquid, saved at 4 DEG C.
Embodiment 2
Utilize the method for bromoacetonitrile and 1- methylimidazole preparation carbon dots, comprising the following steps:
(1) 5mL bromoacetonitrile and 10mL 1- methylimidazole are measured respectively, is poured into 50mL beaker, are stirred rapidly, are made solution
It is uniformly mixed, stands reaction to get reaction solution, carbon dots are contained in reaction solution；
(2) it by after reaction solution natural cooling obtained by step (1), is centrifuged under 8000rpm speed in supercentrifuge
10min obtains supernatant；Then the filtering with microporous membrane for being 0.22 μm by supernatant filter membrane, filtrate are with molecular cut off again
After the bag filter dialysis 48h of 500Da, freeze-drying obtains carbon dots powder；A part of carbon dots powder is finally taken to use ultrapure water respectively
Disperse with ethyl alcohol, obtains carbon dots dispersion liquid, saved at 4 DEG C.
Embodiment 3
Utilize the method for bromoacetonitrile and 1- methylimidazole preparation carbon dots, comprising the following steps:
(1) 5mL bromoacetonitrile and 5mL 1- methylimidazole are measured respectively, is poured into 50mL beaker, is stirred rapidly, keep solution mixed
It closes uniformly, stands reaction to get reaction solution, carbon dots are contained in reaction solution；
(2) it by after reaction solution natural cooling obtained by step (1), is centrifuged under 8000rpm speed in supercentrifuge
10min obtains supernatant；Then the filtering with microporous membrane for being 0.22 μm by supernatant filter membrane, filtrate are with molecular cut off again
After the bag filter dialysis 48h of 500Da, freeze-drying obtains carbon dots powder；A part of carbon dots powder is finally taken to use ultrapure water respectively
Disperse with ethyl alcohol, obtains carbon dots dispersion liquid, saved at 4 DEG C.
Carbon dots obtained are characterized:
Fig. 1 is the transmission electron microscope figure of the obtained carbon dots of the present invention.Morphology analysis is carried out it is found that carbon to carbon dots by Fig. 1
Point is spherical, and size is uniform.
Fig. 2 is the histogram of particle size distribution of the obtained carbon dots of the present invention, and as seen from the figure, the average grain diameter of carbon dots is 17.9nm,
Particle size distribution range is 12-22nm.
Fig. 3 is the uv absorption spectra of the obtained carbon dots of the present invention, and carbon dots have an apparent absorption in 285nm or so
Peak is π-π*Core carbon transition.
Fig. 4 is obtained emission spectrum of the carbon dots under different excitation wavelengths of the present invention, and maximum excitation wavelength is 380nm, right
The launch wavelength answered is 455nm, and strong blue-fluorescence is shown under burst of ultraviolel, and shows as excitation and rely on fluorescence.With
Excitation wavelength increase, emit red shift.
Quantum yield analysis:
The Relative quantum yields of the obtained carbon dots of the embodiment of the present invention 1~3 are measured, it is using quinine sulfate as reference substance, its is molten
Solution is in 0.1M H2SO4In solution, the fluorescence quantum yield when excitation wavelength is 360nm is 54%.The specific method is as follows: first needing
The carbon dots solution and quinine sulfate solution for configuring certain low concentration test their ultraviolet-visible spectrum absorptions at 360nm
Value, adjusting concentration makes the absorption value less than 0.1, and corresponding fluorescence emission spectral peak area is then tested in Fluorescence Spectrometer
(Fig. 5 and Fig. 6).After testing five various concentrations repeatedly, mutual corresponding fluorescence spectrum peak area and ultraviolet-visible light can be obtained
Absorption value is composed, its slope is sought in mapping.Relative quantum yields can be calculated by following formula:
Φx=Φst(Ix/Ist)(ηx/ηst)2
Wherein Φ represents quantum yield；η be solvent related coefficient (dehydrated alcohol 1.36,0.1M dilution heat of sulfuric acid are
1.33)；I represents fluorescence emission spectral peak area and corresponding ultraviolet-visible spectrum absorption value slope ratio；Subscript " x " and
" st " respectively corresponds carbon dots sample and fluorescence reference standard, and the results are shown in Table 1.
The quantum yield test data of table 1, carbon dots
The results show that the carbon dots that average grain diameter is 17.9nm can be obtained using the method for the embodiment of the present invention 1~3,
Quantum yield is 21%.This method can directly react under room temperature (5~40 DEG C), be not necessarily to additional energy consumption, and green is friendly, and anti-
It is short between seasonable, under conditions of reaction system is greater than 30ml, carbon dots are generated in second grade i.e. reaction, and with the body of reaction system
Product increases, and the reaction time shortens, therefore goal of the invention is can be realized greater than 1s in reaction time control, searches out for carbon dots synthesis
New synthetic method.
Embodiment 4
Utilize the method for bromoacetonitrile and 1- vinyl imidazole preparation carbon dots, comprising the following steps:
(1) 5mL bromoacetonitrile and 5mL 1- vinyl imidazole are measured respectively, is poured into 50mL beaker, are stirred rapidly, are made solution
It is uniformly mixed, stands reaction to get reaction solution, carbon dots are contained in reaction solution；
(2) it by after reaction solution natural cooling obtained by step (1), is centrifuged under 8000rpm speed in supercentrifuge
10min obtains supernatant；Then the filtering with microporous membrane for being 0.22 μm by supernatant filter membrane, filtrate are with molecular cut off again
After the bag filter dialysis 48h of 500Da, freeze-drying obtains carbon dots powder；A part of carbon dots powder is finally taken to use ultrapure water respectively
Disperse with ethyl alcohol, obtains carbon dots dispersion liquid, saved at 4 DEG C.
The time control reacted in the present embodiment is being greater than 1s, and temperature control is achievable within the scope of 5~40 DEG C；Bromine second
Nitrile and 1- vinyl imidazole volume ratio are controlled can be achieved in 1:1~1:3.
Carbon dots obtained are characterized:
Fig. 7 is the uv absorption spectra that carbon dots are made in the present embodiment, and carbon dots have an apparent suction in 260nm or so
Peak is received, is π-π*Core carbon transition.
Fig. 8 is that emission spectrum of the carbon dots under different excitation wavelengths is made in the present embodiment, and maximum excitation wavelength is 380nm,
Corresponding launch wavelength is 465nm, and strong blue-fluorescence is shown under burst of ultraviolel.
The quantum yield and embodiment 1 that carbon dots are made in the present embodiment quite, show bromoacetonitrile and 1- vinyl imidazole or 1-
Carbon dots can be made in the glyoxaline compounds such as methylimidazole.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (10)
1. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots, it is characterised in that: by bromoacetonitrile and imidazoles chemical combination
It is directly reacted after object mixing, carbon dots is made.
2. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1, it is characterised in that: described
Glyoxaline compound is at least one of 1- vinyl imidazole or 1- methylimidazole.
3. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1, it is characterised in that: described
Bromoacetonitrile is that 1:1~1:3 is mixed with glyoxaline compound by volume.
4. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1, it is characterised in that: described
The temperature of reaction is 5~40 DEG C.
5. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1, it is characterised in that: described
Mixing uses agitating mode.
6. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1, it is characterised in that: described
The time of reaction is at least 1s.
7. any one method using bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 1~6, feature
It is: further includes that carbon dots are collected after the reaction, it is specially that reaction solution is cooling, it is centrifuged, filters, carbon dots powder is lyophilized to obtain in dialysis
End.
8. utilizing the method for bromoacetonitrile and glyoxaline compound preparation carbon dots according to claim 7, it is characterised in that: described
Centrifugation is in 10~20min of 8000rpm centrifugation；It is described to be filtered into the filtering with microporous membrane with 0.22 μm；The dialysis cuts to use
Stay 24~48h of bag filter dialysis that molecular weight is 500Da.
9. utilizing carbon dots made from according to any one of claims 1 to 88 described in any item methods.
10. carbon dots according to claim 9, it is characterised in that: the average grain diameter is 17.9nm；Particle size distribution range
12-22 is nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112113944A (en) * | 2020-09-30 | 2020-12-22 | 江南大学 | Preparation of emission spectrum variable carbon dots and application thereof in detection of pH value |
| CN114989820A (en) * | 2022-05-31 | 2022-09-02 | 哈尔滨工程大学 | Construction method of carbazolyl fluorescent carbon dots with large Stokes displacement |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315993A (en) * | 2014-07-22 | 2016-02-10 | 中国科学院兰州化学物理研究所 | Preparation method for ionic-liquid-modified carbon quantum dot |
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- 2019-07-31 CN CN201910701856.4A patent/CN110317606B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315993A (en) * | 2014-07-22 | 2016-02-10 | 中国科学院兰州化学物理研究所 | Preparation method for ionic-liquid-modified carbon quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| FUSHUANG NIU等: "Bottom-up electrochemical preparation of solid-state carbon nanodots directly from nitriles/ionic liquids using carbon-free electrodes and the applications in specific ferric ion detection and cell imaging", 《NANOSCALE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112113944A (en) * | 2020-09-30 | 2020-12-22 | 江南大学 | Preparation of emission spectrum variable carbon dots and application thereof in detection of pH value |
| CN114989820A (en) * | 2022-05-31 | 2022-09-02 | 哈尔滨工程大学 | Construction method of carbazolyl fluorescent carbon dots with large Stokes displacement |
| CN114989820B (en) * | 2022-05-31 | 2024-03-26 | 哈尔滨工程大学 | Construction method of carbazolyl fluorescent carbon dots with large Stokes displacement |
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