CN105271172A - Preparation method of super-high-quantum-yield carbon quantum dots with citric acid-urea as raw materials - Google Patents
Preparation method of super-high-quantum-yield carbon quantum dots with citric acid-urea as raw materials Download PDFInfo
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Abstract
The invention relates to a preparation method of super-high-quantum-yield carbon quantum dots with citric acid-urea as raw materials. The preparation method includes the steps that citric acid and urea serve as the raw materials for a hydrothermal reaction, a hydrothermal product is obtained and dried, pyrolysis calcination is conducted, and a calcined product is obtained; the calcined product is ground and filtered, and then the super-high-quantum-yield carbon quantum dots are obtained. The preparation method is mild in reaction condition and easy and convenient to operate, and the raw materials are easy to obtain, cheap and environmentally friendly. The prepared carbon quantum dots are high in quantum efficiency, good in monodispersity, stable in luminescent performance, free of twinkling phenomena, good in biocompatibility and the like.
Description
Technical field
The invention belongs to the preparation field of carbon quantum dot, particularly a kind of with the preparation method of citric acid-urea superelevation quantum yield carbon quantum dot that is raw material.
Background technology
In recent years, due to tradition provide fluorescence dye to be subject to repeated multiple times exciting after be easy to photobleaching thus fluorescence property weakens, to its have similar light conversion properties can semiconductor-quantum-point be more and more applied in biomarker and scientific research material.But traditional semiconductor-quantum-point is heavy metal quantum dot often, the shortcomings such as its intrinsic physiologically acceptable performance difference and easily " light nictation " phenomenon have had a strong impact on the expansion of its range of application.Except these shortcomings, the intrinsic bio-toxicity of traditional mark substance limits its amount of adding and some mark substance quantum yields are not high, so this has just had a strong impact on their application in biomarker.Therefore, increasing research starts to pay close attention to inorganic non-metallic carbon granule quantum dot.First, carbon granule quantum dot not only overcomes the shortcoming of conventional tag material, and have good biocompatibility and unglazed nictation phenomenon etc. advantage.Therefore, the most excellent material of the inorganic non-metallic carbon granule quantum dot current research application aspect such as biomarker, biological detection, bioprobe just.
The synthetic method of current inorganic non-metallic carbon quantum dot mainly contains two kinds, a kind of is synthetic method from top to bottom: pulverize carbon source, make it effectively luminous by the mode of polymer surfaces passivation, mainly comprise arc discharge method, laser method, electrochemical process, mechanical disintegration, ball milling or chemical oxidation.Although carbon point size uniformity prepared by this method is higher, consume energy too high, the carbon point fluorescent yield that except laser burns method prepared by additive method is all lower.Another method is synthetic method from top to bottom: pyrolysis or the suitable precursor of carbonization directly synthesize fluorescent carbon quantum dot, comprises oxidation or etch, pyrolysis organism method, microwave process for synthesizing, ultrasonic method, the doping method of ashes.But the quantum yield of the carbon quantum dot of being produced by the major part in these methods is often lower, this will when biomarker the amount of increasing input, cause toxicity to improve.Therefore, find a kind of can prepare there is superelevation quantum yield, the method for carbon point of uniform particle sizes has considerable meaning.
High temperature pyrolytic cracking (HTP) is fluorescent carbon point preparation method conventional at present.Currently reported, prepare fluorescent carbon point by each seed amino acid of microwave-heating, but there is microwave temperature uncontrollable (there is local hot spots) and the shortcoming such as fluorescence efficiency is not high.Prepare fluorescent carbon point by hydrothermal method and not only there is nucleation evenly, the advantage that granular size is controlled, but not high by the most of fluorescent yield of this method carbon granule quantum dot in current report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of with the preparation method of Trisodium Citrate-urea superelevation quantum yield quantum dot that is raw material, and the method is simple and easy to do, and cost is lower; The carbon quantum dot that the method prepares has that quantum yield is high, monodispersity good, stable luminescent property, " nictation " advantage such as phenomenon, good biocompatibility does not occur.
Of the present invention a kind of with the preparation method of citric acid-urea superelevation quantum yield carbon quantum dot that is raw material, comprising:
(1) carry out hydro-thermal reaction with citric acid and urea for raw material, obtain hydrothermal product; Wherein, hydrothermal temperature is 80 ~ 260 DEG C, and the reaction times is 0.5h ~ 3h;
(2), after the hydrothermal product in step (1) being dried, carry out pyrolysis calcining, obtain calcinate; Wherein, the temperature of calcining is 100 ~ 500 DEG C, and calcination time is 0.1 ~ 2h;
(3) product of calcining in step (2) is ground, filter, the superelevation quantum yield carbon quantum dot that to obtain with citric acid-urea be raw material.
During for biological aspect application, with the dialysis of 3000Da ~ 3500Da dialysis membrane, extracellular fluid dialysis is for subsequent use; Wherein dialysis time is 12h.
In described step (1), the mass ratio of citric acid, urea and distilled water is 1 ~ 10g:0.01 ~ 100g:0.01 ~ 100g.
Drying in described step (2) is 60 DEG C of oven dry of spending the night.
In described step (2), during calcining, temperature rise rate is 10 DEG C/min.
0.22 μm of water system membrane filtration is filtered in described step (3).
Use citric acid to be carbon source in the present invention, take urea as nitrogenous source, under water surrounding, carry out hydro-thermal reaction.Because this reaction is homogeneous reaction, so the size of nucleation is homogeneous.Then make the further carbonization of hydrothermal product that its water absorbability and adhesive are reduced by the method for pyrolysis.The carbon granule quantum dot obtained by this method has superelevation quantum yield, and granular size is homogeneous, unglazed nictation phenomenon, fluorescent stability is high, and synthetic method is simple, the plurality of advantages such as reaction material is cheap and easy to get, and cost is lower.Low cytotoxicity is had concurrently, so carbon point prepared by this patent method only needs a small amount of interpolation can obtain perfect biomarker figure owing to having superelevation quantum yield.These advantages are that citric acid-urea (urea) carbon quantum dot is laid a good foundation in the application of the tradition such as life science, analysis science, Materials science, immune medical science, inspection and quarantine and emerging field.
In method of the present invention with citric acid-urea for raw material hydro-thermal legal system completes preliminary carbonization and the doping of nitrogen for pyrolytic precursors; Hydrothermal product calcining has been carried out continuation carbonization.
Invention is carried out in aqueous phase under middle cold condition, reaction conditions is comparatively gentle, easy and simple to handle, raw material is easy to get cheaply, environmental protection, hydro-thermal reaction product itself has comparatively hyperfluorescenceZeng Yongminggaoyingguang, and product yield is higher, and the carbon quantum dot of preparation has that superelevation quantum yield, nothing " light nictation " phenomenon, stability are high, the advantage such as good biocompatibility, pH excellent.
beneficial effect
(1) preparation method of the present invention is simple to operation, reproducible, and cost is low, and the carbon quantum dot shelf time prepared is long;
(2) carbon quantum dot that preparation method of the present invention obtains has that quantum yield high (can reach 78.8%, with Quinine Sulphate Di HC sulphuric acid soln be that the emissive porwer of less than 0.05 for benchmark in its excitation wavelength 360nm place uv-absorbing), monodispersity are good, stable luminescent property, " nictation " advantage such as phenomenon, good biocompatibility does not occur.
Accompanying drawing explanation
Fig. 1 is the preparation method's schema in embodiment 1;
Fig. 2 is the transmission electron microscope picture of carbon granule fluorescence quantum in embodiment 1;
Fig. 3 is the X-ray diffractogram of carbon granule fluorescence quantum in embodiment 1;
Fig. 4 is the fluorescent stability test curve of carbon granule fluorescence quantum in embodiment 1;
Fig. 5 is the fluorescence intensity comparison diagram of embodiment 3 carbon granule fluorescence quantum under different hydro-thermal time (0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h);
Fig. 6 is the fluorescence intensity comparison diagram of carbon granule fluorescence quantum under varying environment pH in embodiment 2.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:20g) are mixed, stirring and dissolving, obtains mixed solution;
(2) mixed solution in (1) is placed in 100mL autoclave, under 170 DEG C of environment, hydro-thermal reaction 1.5h, obtains hydrothermal product;
(3) gained hydrothermal product in (2) to be spent the night under 60 DEG C of environment oven dry;
(4) under gained oven dry product is placed in 250 DEG C of environment in (3), calcine 0.5h, temperature rise rate is 10 DEG C/min, obtains calcinate;
(5) calcinate obtained in (4) is ground abundant distilled water to dissolve, with 0.22 μm of water system membrane filtration, obtain the carbon point solution of uniform particle diameter.
Preparation method's schema as shown in Figure 1.Fig. 2 is the transmission electron microscope picture of carbon granule fluorescence quantum in embodiment 1, and average particle size is about 6.64nm.Fig. 3 is the X-ray diffractogram of carbon granule fluorescence quantum, diffraction peak and Standard graphite crystal formation standard peak position similar.Fig. 4 is the fluorescent stability test curve of carbon granule fluorescence quantum, and the product as can be seen from the figure prepared does not change substantially through the irradiation fluorescence intensity of 1 hour, illustrates that the photoluminescent property of product is highly stable.
Embodiment 2
(1) citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:25g) are mixed, stirring and dissolving, obtains mixed solution;
(2) mixed solution in (1) is placed in 100mL autoclave, under 170 DEG C of environment, hydro-thermal reaction 1.5h, obtains hydrothermal product;
(3) gained hydrothermal product in (2) to be spent the night under 60 DEG C of environment oven dry;
(4) under gained oven dry product is placed in 250 DEG C of environment in (3), calcine 0.5h, temperature rise rate is 10 DEG C/min, obtains calcinate;
(5) calcinate obtained in (4) is ground abundant distilled water to dissolve, with 0.22 μm of water system membrane filtration, obtain the carbon point solution of uniform particle diameter.
Fig. 6 is the fluorescence intensity comparison diagram of carbon granule fluorescence quantum under varying environment pH, and as can be seen from the figure carbon point solution fluorescence intensity when pH is between 4 ~ 6 is the strongest, and having the application of pH special effects may.
Embodiment 3
(1) citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:20g) are mixed, stirring and dissolving, obtains mixed solution;
(2) mixed solution in (1) is placed in 100mL autoclave, under 170 DEG C of environment, hydro-thermal reaction 0.5 ~ 3h, obtains hydrothermal product;
(3) gained hydrothermal product in (2) to be spent the night under 60 DEG C of environment oven dry;
(4) under gained oven dry product is placed in 300 DEG C of environment in (3), calcine 1h, temperature rise rate is 10 DEG C/min, obtains calcinate;
(5) calcinate obtained in (4) is ground abundant distilled water to dissolve, with 0.22 μm of water system membrane filtration, obtain the carbon point solution of uniform particle diameter.
Fig. 5 is that hydro-thermal-pyrolysis two-step approach prepares the fluorescence intensity comparison diagram of citric acid-urea (urea) carbon granule fluorescence quantum under different hydro-thermal time (0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h), even if as can be seen from the figure reduced decades of times fluorescence equipment power, the fluorescence intensity of product is still so strong.
Claims (4)
1., with a preparation method for citric acid-urea superelevation quantum yield carbon quantum dot that is raw material, comprising:
(1) carry out hydro-thermal reaction with citric acid and urea for raw material, obtain hydrothermal product; Wherein, hydrothermal temperature is 80 ~ 260 DEG C, and the reaction times is 0.5h ~ 3h;
(2), after the hydrothermal product in step (1) being dried, carry out pyrolysis calcining, obtain calcinate; Wherein, the temperature of calcining is 100 ~ 500 DEG C, and calcination time is 0.1 ~ 2h;
(3) product of calcining in step (2) is ground, filter, the superelevation quantum yield carbon quantum dot that to obtain with citric acid-urea be raw material.
2. according to claim 1 a kind of with the preparation method of citric acid-urea superelevation quantum yield carbon quantum dot that is raw material, it is characterized in that, in described step (1), the mass ratio of citric acid, urea and distilled water is 1 ~ 10g:0.01 ~ 100g:0.01 ~ 100g.
3. according to claim 1 a kind of with the preparation method of citric acid-urea superelevation quantum yield carbon quantum dot that is raw material, it is characterized in that, in described step (2), during calcining, temperature rise rate is 10 DEG C/min.
4. according to claim 1 a kind of with the preparation method of citric acid-urea superelevation quantum yield carbon quantum dot that is raw material, it is characterized in that, in described step (3), be filtered into 0.22 μm of water system membrane filtration.
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| CN106433632B (en) * | 2016-10-08 | 2019-06-25 | 哈尔滨师范大学 | A kind of preparation method and applications of carbon quantum dot |
| CN106433632A (en) * | 2016-10-08 | 2017-02-22 | 哈尔滨师范大学 | Preparation method and application of carbon quantum dot |
| CN107522190A (en) * | 2017-07-31 | 2017-12-29 | 泰山医学院 | A kind of synthetic method of carbon quantum dot |
| CN109181689A (en) * | 2018-09-26 | 2019-01-11 | 东华大学 | A kind of preparation method of photochromic adjustable hydrophobicity N doping fluorescent carbon point |
| CN109179377A (en) * | 2018-09-26 | 2019-01-11 | 东华大学 | A kind of preparation method of hydrophobic fluorescence carbon dots |
| CN109179377B (en) * | 2018-09-26 | 2021-11-09 | 东华大学 | Preparation method of hydrophobic fluorescent carbon dots |
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| CN110835104A (en) * | 2019-10-28 | 2020-02-25 | 深圳先进技术研究院 | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery |
| CN111073638A (en) * | 2019-12-19 | 2020-04-28 | 东华大学 | Method for preparing controllable photoluminescence carbon dots by changing temperature |
| CN111234817A (en) * | 2020-03-02 | 2020-06-05 | 太原理工大学 | Carbon dots with high thermal stability and preparation method thereof |
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