CN101787278B - Pyrolytic synthesis method for water-soluble fluorescent carbon nano-particles - Google Patents
Pyrolytic synthesis method for water-soluble fluorescent carbon nano-particles Download PDFInfo
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Abstract
The invention relates to a pyrolytic synthesis method for water-soluble fluorescent carbon nano-particles, which belongs to the technical field of nano-carbon material preparation processes. A main process of the method comprises: calcining ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) or ethylenediaminetetraacetic acid tetrasodium salt (EDTA-4Na) sold on market in a tube furnace under the protection of N2 gas at 400 DEG C for 2 to 3 hours; grinding a sample into powder after calcination; dissolving the obtained powder in a certain amount of ethanol; placing the obtained product in an ultrasonic oscillator for 5 to 10 minutes of ultrasonic treatment; performing high-speed ion separation to obtain supernatant; subjecting the supernatant to rotary evaporation to obtain concentrated solution; pouring the concentrated solution into a beaker; and putting the beaker into an oven for drying so as to obtain the water-soluble fluorescent carbon nano-particles. The product of the invention can be applicable to the field of biomedicine and the application field of luminescent electronic devices.
Description
Technical field
The present invention relates to a kind of pyrolytic synthesis method of water-soluble fluorescent carbon nano-particles, belong to nano-carbon material fabricating technology field.
Background technology
Fluorescent nano material is widely used in the fluorescent mark of technique of display, semiconductor lighting, laser apparatus and cell.Wherein, fluorescent nano material enjoys the great attention of scientific and technological circle in bio-medical applications.The semiconductor-quantum-point fluorescent material that with CdSe is representative is to be used as the fluorescence observation that fluorescent probe is applied to cell the earliest.Yet,, find that this type material is not suitable for clinical application (fluorescence observation of active somatic cell) along with the assessment of biological effect.Main worry is wherein to contain pair cell very supervirulent metals ion is arranged.This is that the semiconductor-quantum-point fluorescent material is applied to the challenge that biological field is difficult to overcome.On the other hand, the semiconductor-quantum-point fluorescence efficiency is difficult to keep stable.Surface stabilizer is easy to desorption and causes quantum dot to be reunited, and fluorescence efficiency sharply descends.Their preservation also is a difficult problem, can only be kept at usually in the solution, and time one length will be condensed, and is no longer solvable, and fluorescence is seriously decayed.In addition, the semiconductor-quantum-point of highly luminescent is generally oil loving, can not directly apply to living things system.Therefore, preparation have low toxicity in addition nontoxic, fluorescence is stable, can be for a long time with solid-state form do not have reunite deposit, fluorescent yield is high, peak width is narrow, the novel fluorescence nano material that is easy to advantage such as physiologically acceptable has been represented current nano materials research an important development direction.
Compare with quantum dot, fluorescent carbon nano-particles has superior biocompatibility and hypotoxicity, and the pair cell damage is little, especially has special advantages at the living body biological mark.Compare with the organic-biological dyestuff, the fluorescence carbon material has higher stability, and anti-photobleaching property is strong.Therefore, fluorescent carbon nano-particles is one of ideal biological fluorescent labelling material.In recent years, because the special advantages of fluorescent carbon nano-particles, the scientific worker has studied the synthetic fluorescent carbon nano-particles of multiple preparation method.2006, Chinese American Sun Ya duckweed seminar found, after multistep aftertreatment (the surface-functionalized processing such as the polymkeric substance that are similar to the carbon pipe after the strong acid oxidation again wrap up), can stablize emitting fluorescence with the enough little carbon nano-particles of laser ablation graphite generation.Mao Chengde group is a precursor with non-luminous candle ash particle; Obtained the water miscible fluorescent carbon nano-particles that has only 1 nanometer little with the way of strong acid oxidation, very utilized similar method successfully from the Sweet natural gas ash, to isolate the luminous carbon nanoparticle about 5 nanometers near Chen etc.Fourth will peak group is a precursor with the carbon nanotube, utilizes electrochemical treatment to prepare the carbon nano-crystal of the fluorescence of even size.Gogotsi seminar utilizes the strong acid oxidation, and the method for surface graft ODA obtains the diamond nano particulate of oil-soluble emission blue-fluorescence.Li etc. utilize silicon-dioxide to be template, and the precursor of growth in situ carbon on silicon-dioxide obtains the carbon nanoparticle through the pyrolytic method then, and obtaining through the polymkeric substance parcel can effectively luminous fluorescent carbon nano-particles again.Giannelis seminar synthesizes the oil-soluble agraphitic carbon nanoparticle of stearylamine parcel at 300 ℃ of calcining stearylamines and Citrate trianion mixing precursor.With Citrate trianion and HOCH
2CH
2OCH
2CH
2NH
2Be precursor, be dissolved in earlier in the aqueous solution that water miscible decolorizing carbon nanoparticle is prepared in calcining behind the evaporate to dryness.Although the preparation method is simple, quantum yield is lower, about 3%.The quantum yield of the fluorescence carbon nanoparticle of bibliographical information is as shown in table 1 below at present:
Table 1 is the quantum yield of the fluorescence carbon nanoparticle of bibliographical information at present
| Seminar | Sun Yaping | Mao Chengde | Chen | Ding Zhifeng | Li | Giannelis |
| Quantum yield | 10％ | 2％ | 0.43％ | 6％ | 14.7％ | 3％ |
Up to the present, the best result of the fluorescence quantum yield of report is no more than 15% (seeing table 1), and half-peak is roomy to more than 100 nanometers.This statement of facts, synthesizing of the carbon nano-particles of high-efficiency fluorescence exists very big challenge really.These methods all are not suitable for mass preparation, need complicated aftertreatment, and some is handled like the strong acid oxidation, and expensive equipment and reagent etc. are compared in also having used of having.Therefore, development effectively, simple, cheap, safety, large-scale preparation method is particularly important.
Summary of the invention
The pyrolytic synthesis method that the purpose of this invention is to provide a kind of water-soluble fluorescent carbon nano-particles.
The pyrolytic synthesis method of a kind of water-soluble fluorescent carbon nano-particles of the present invention is characterized in that having following technological process and step:
A. take by weighing a certain amount of ethylenediamine tetraacetic ethanol disodium salt (EDTA-2Na) or tetrasodium salt of EDTA (EDTA-4Na) is placed in the quartz boat, be placed down in the tube furnace in the N2 gas shiled and calcine, calcining temperature is 400 ℃, and calcination time is 2～3 hours; Heat-up rate is 10 ℃/min; After the calcining with the sample mill powdered;
B. the above-mentioned powder that obtains was annealed 15 minutes down at 400 ℃ once more; Perhaps, get into next step without high temperature annealing;
C. with the gained powder dissolution in a certain amount of ethanol, and placed the ultrasonator supersound process 5～10 minutes; High speed centrifugation separates then, and the rotating speed of supercentrifuge is 15000 rev/mins; Obtain upper strata liquid; Repeat 2～3 times, collect upper strata liquid; Rotary evaporation concentrates it then;
D. above-mentioned gained liquid concentrator is poured in the beaker, and it is dry to put into baking oven, temperature is 60～80 ℃, and drying time is 7～16 hours, finally obtains water-soluble fluorescent carbon nano-particles.
The formation mechanism of water-soluble fluorescent carbon nano-particles is among the present invention: under nitrogen and hot conditions, the raw material disodium edta carries out the pyrolysis carbonization, owing to have-stabilization of COONa group, it is certain water-soluble that pyrolysis product keeps in water.
The source of raw material disodium edta among the present invention is available from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group
The characteristics and the advantage of the inventive method are described below:
The present invention is through using N
2Calcine the EDTA sodium salt under the protection under the certain temperature and prepare water-soluble fluorescent carbon nano-particles, calcination process is pollution-free, and can efficiently prepare the fluorescent carbon nano-particles that can stablize the emission blue light, have the sub-productive rate of present report maximum amount (40%) fast.It is precursor that the present invention adopts the EDTA sodium salt, and process method is simple, does not have any intermediate product, easy to operate, can realize suitability for industrialized production.The water-soluble fluorescent carbon nano-particles that utilizes the inventive method to prepare is fit to be applied to the application of biomedical sector (like the fluorescent mark and the in vivo marker of cell) and emitting electron device (LED).
The advantage of the inventive method is: adopt precursor raw material EDTA sodium salt, it is cheap, in calcination process, does not discharge environmental pollutant, belongs to environmentally friendly preparation technology; The fluorescent carbon nano-particles of preparing can be stablized the blue-fluorescence of emission high quantum production rate.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) the photo figure of the fluorescent carbon nano-particles that prepared by EDTA-2Na (a) and EDTA-4Na (b) among the present invention.
Fig. 2 is the uv-visible absorption spectra figure and the fluorescence spectrum figure of the fluorescent carbon nano-particles that prepared by EDTA-2Na (a) and EDTA-4Na (b) among the present invention.
Fig. 3 among the present invention by the fluorescent carbon nano-particles of EDTA-2Na (left side) and EDTA-4Na (right side) preparation and Quinine Sulphate Di HC (0.05mol/L, quantum yield are 0.54) ultraviolet-visible absorption and fluorescence curve.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment 1: the concrete preparation process of present embodiment is following:
(1) at first, take by weighing the EDTA-2Na of 1.0g, it evenly is tiled in the bottom of quartz boat with electronic balance.
(2) quartz boat is put into tube furnace, N
2Protect following 400 ℃ the calcining 2h, 10 ℃/min of heat-up rate, after the calcining with the sample mill powdered.
(3) powder that obtains evenly is tiled in the quartz boat bottom, puts into tube furnace, the following 400 ℃ of annealing 15min of air take out quartz boat then, and sample powder is collected in the cooling back.
(4) powder that obtains is dissolved in the 10mL ethanol, placed ultrasonator ultrasonic 5～10 minutes, high speed centrifugation (15000 rev/mins) gets upper strata liquid, repeats 2-3 time, and rotary evaporation concentrates (containing small amount of ethanol) with upper strata liquid.
(5) liquid concentrator is poured in the 50mL beaker, be placed on drying in the baking oven, temperature is 60～80 ℃, and drying time is 7～16 hours, finally obtains the water soluble fluorescence carbon nano-particle.
Embodiment 2: the concrete preparation process of present embodiment is following:
(1) at first, take by weighing the EDTA-4Na of 1.0g, it evenly is tiled in the bottom of quartz boat with electronic balance.
(2) quartz boat is put into tube furnace, N
2Protect following 400 ℃ the calcining 2h, 10 ℃/min of heat-up rate, after the calcining with the sample mill powdered.
(3) powder that obtains is dissolved in the 10mL ethanol, placed ultrasonator ultrasonic 5～10 minutes, high speed centrifugation (15000 rev/mins) gets upper strata liquid, repeats 2-3 time, collects upper strata liquid, and rotary evaporation concentrates (containing small amount of ethanol) with it.
(4) liquid concentrator is poured in the 50mL beaker, be placed on drying in the baking oven, temperature is 60～80 ℃, and drying time is 7～16 hours, finally obtains the water soluble fluorescence carbon nano-particle.
Used raw material EDTA-2Na and EDTA-4Na are all available from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group in the foregoing description.
Instrument detecting to embodiment gained sample
(1) detection of transmission electricity electron microscope (TEM)
Characterize the pattern of different EDTA sodium salt synthetic fluorescent carbon nano-particles with TEM.The result shows with EDTA-2Na and EDTA-4Na synthetic carbon nano-particles size all less than 10nm, and has good dispersiveness.Referring to Fig. 1.
(2) detection of ultraviolet-visible spectrophotometer and spectrophotofluorometer
Characterize the optical property of different EDTA sodium salt synthetic fluorescent carbon nano-particles with ultraviolet-visible spectrophotometer and spectrophotofluorometer.The result show two kinds of carbon nano-particles all～the 320nm place is by tangible absorption peak, fluorescence emission peak is positioned at～400nm, peak width at half is respectively 60nm and 55nm.The carbon nano-particles that is prepared by these two kinds of precursors excites down at 320nm, can observe bright blueness (bluish voilet) fluorescence.Referring to Fig. 2.
(3) measurement of fluorescent carbon nano-particles quantum yield
In measurement, adopting Quinine Sulphate Di HC (0.05M/L) is reference standard (its quantum yield is 54%).At first, difference carbon determination nano-particle solution and Quinine Sulphate Di HC solution excitation wavelength absorbancy.Then, measure the fluorescence emission peak of quantum dot and Quinine Sulphate Di HC respectively, and integration obtains the fluorescence peak area.Calculate fluorescence quantum yield according to following formula again:
QYs＝QYr(Fs/Fr)(Ar/As)(ηs/ηr)
2
F
s(sample) and F
r(reference material) is the fluorescent emission peak area, A
s(sample) and A
r(reference material) is ultraviolet absorptivity under excitation wavelength, η
s(sample) and η
r(reference material) is the specific refractory power of solvent.QY
sAnd QY
rBe respectively sample and test substance quantum yield.Draw at last, the fluorescent carbon nano-particles quantum yield of being prepared by EDTA-2Na is 40.64%, and the fluorescent carbon nano-particles quantum yield of being prepared by EDTA-4Na is 40.17%.Referring to Fig. 3.
Claims (1)
1. the pyrolytic synthesis method of a water-soluble fluorescent carbon nano-particles is characterized in that having following technological process and step:
A. take by weighing a certain amount of disodium EDTA or tetrasodium salt of EDTA and be placed in the quartz boat, at N
2Gas shiled is placed down in the tube furnace and calcines, and calcining temperature is 400 ℃, and calcination time is 2～3 hours; Heat-up rate is 10 ℃/min; After the calcining with the sample mill powdered;
B. the above-mentioned powder that obtains was annealed 15 minutes down at 400 ℃ once more; Perhaps, get into next step without annealing;
C. with the gained powder dissolution in a certain amount of ethanol, and placed the ultrasonator supersound process 5～10 minutes; High speed centrifugation separates then, and the rotating speed of supercentrifuge is 15000 rev/mins; Obtain upper strata liquid; Repeat 2～3 times, collect upper strata liquid; Rotary evaporation concentrates it then;
D. above-mentioned gained liquid concentrator is poured in the beaker, and it is dry to put into baking oven, temperature is 60～80 ℃, and drying time is 7～16 hours, finally obtains water-soluble fluorescent carbon nano-particles.
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| CN102173405B (en) * | 2010-12-24 | 2012-08-22 | 苏州方昇光电装备技术有限公司 | Preparation method of carbon nanoparticle with controllable photoluminescence |
| CN102134485B (en) * | 2010-12-24 | 2013-10-02 | 苏州方昇光电装备技术有限公司 | Method for mass production of water-soluble fluorescent carbon nanoparticles |
| CN105273715B (en) * | 2015-10-29 | 2017-08-01 | 东华大学 | A kind of continuous method for preparing fluorescence carbon nano-particle |
| CN105757466A (en) * | 2016-03-09 | 2016-07-13 | 沈阳大学 | Manufacturing method of carbon nano-particle fluorescent ice lamp |
| CN105838364B (en) * | 2016-04-29 | 2018-03-27 | 济南大学 | A kind of method for being pyrolyzed ammonium carboxylate salt and preparing fluorescent carbon point |
| CN109111919A (en) * | 2018-09-30 | 2019-01-01 | 湖北大学 | A kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products |
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