CN105802623A - Method achieving super-high-yield synthesizing of nitrogen-doped fluorescent carbon nanodots - Google Patents
Method achieving super-high-yield synthesizing of nitrogen-doped fluorescent carbon nanodots Download PDFInfo
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Abstract
The invention discloses a method achieving super-high-yield synthesizing of nitrogen-doped fluorescent carbon nanodots, and belongs to the technical field of carbon nanomaterial synthesizing. The invention aims at solving the problem that an existing method for preparing fluorescent carbon nanodots is low in synthetic yield. The synthesizing method of the nitrogen-doped fluorescent carbon nanodots comprises the following steps that chitosan and amide containing unsaturated double bonds or carboxylic acid containing unsaturated double bonds or long-chain fatty acid containing unsaturated double bonds are put into ultrapure water, hydrothermal carbonization is conducted, high-speed centrifugal separation, dialysis and freeze-drying treatment are sequentially conducted, and a nitrogen-doped fluorescent carbon nanodot solid can be obtained. According to the method achieving super-high-yield synthesizing of the nitrogen-doped fluorescent carbon nanodots, the synthetic yield reaches up to 90%.
Description
Technical field
The invention belongs to nano-carbon material synthesis technical field, be specifically related to high yield synthesis fluorescent carbon nano material.
Background technology
Compared to traditional semiconductor-quantum-point (such as CdS, PbS and CdSe) toxicity is big, synthesis cost is high, fluorescent carbon nano dot is widely used in living body biological imaging due to features such as the fluorescence property of its brilliance, biocompatibility and light uniform stabilities, the field such as opto-electronic conversion and luminescent device (AdvancedMaterials, 2012,24 (15), 2037-2041).As one of fluorescent nano material, fluorescent carbon nano dot also has carbon source kind to be enriched and the low feature of cost.
Owing to fluorescent carbon nano dot is widely used field, thus high yield synthesis fluorescent carbon nano dot becomes study hotspot.The synthetic yield of fluorescent carbon nano dot=(fluorescent carbon nano dot quality/presoma quality) × 100%.Current fluorescent carbon nano dot still suffers from the problem that synthetic yield is low: the productivity as being precursor synthesis fluorescent carbon nano dot with little molecule sucrose is 41.8% (Nanoscale, 2013,5,1967-1971)；Little molecule aminoacid/glucose be the productivity of precursor synthesis fluorescent carbon nano dot be 25% (ScientificReports, 2014,35 (6) 233-237)；It is 30% (Adv.Sci.2015,1500002) with the productivity that biomass pollen is precursor synthesis fluorescent carbon nano dot；It is 1.6% (AdvancedMaterials, 2012,24 (15), 2037-2041) with the productivity that biomass grass is precursor synthesis fluorescent carbon nano dot；With the productivity that changing food waste is precursor synthesis fluorescent carbon nano dot be 0.1% (ACSAppl.Mater.Interfaces, 2014,6 (5), 3365-3370).The synthetic yield adopting at present prior art synthesis fluorescence nano carbon point is usually less than 50%, and the research of ultra-high yield (more than 50%) synthesis fluorescent carbon nano dot there is not been reported.
Summary of the invention
The invention solves the problems that the problem that the existing synthetic yield preparing fluorescent carbon nano dot method is low, and a kind of method providing ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot.
The present invention is with chitosan and amide containing unsaturated double-bond (or the carboxylic acid containing unsaturated double-bond, or the long-chain fatty acid containing unsaturated double-bond) for fluorescent carbon nano dot presoma, adopt hydrothermal carbonization to obtain the synthetic yield N doping fluorescent carbon nano dot up to 90%.
For solving above-mentioned technical problem, the solution of the present invention is as follows: a kind of method of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot is completed by following step: by chitosan and amide (or the carboxylic acid containing unsaturated double-bond containing unsaturated double-bond, or the long-chain fatty acid containing unsaturated double-bond) be placed in ultra-pure water, sequentially pass through high speed centrifugation after carrying out hydrothermal carbonization again to separate, dialyse and frozen dried, N doping fluorescent carbon nano dot solid can be obtained.
The mol ratio of described chitosan and the amide (or the carboxylic acid containing unsaturated double-bond, or the long-chain fatty acid containing unsaturated double-bond) containing unsaturated double-bond is (0.01～1): 1.
The described amide containing unsaturated double-bond is N-DMAA, NIPA, acrylamide or n-methylolacrylamide, or the amide compound (compound tense is mixed by any ratio) of above-mentioned unsaturated double-bond.
The described carboxylic acid containing unsaturated double-bond includes the carboxylic acid compound (compound tense is mixed by any ratio) of .beta.-methylacrylic acid, acrylic acid, methacrylic acid, cinnamic acid, acrylic acid methyl ester., fumaric acid, maleic anhydride or maleic acid, or above-mentioned unsaturated double-bond.
The described long-chain fatty acid containing unsaturated double-bond is linolenic acid, linoleic acid, sad, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid or arachidic acid etc., or the carboxylic acid compound (compound tense is mixed by any ratio) of above-mentioned unsaturated double-bond.
Described chitosan and the gross mass of amide (or the carboxylic acid containing unsaturated double-bond, or the long-chain fatty acid containing unsaturated double-bond) containing unsaturated double-bond are (60～210) mg:1mL with the volume ratio of water.
180～220 DEG C of hot carbonizations of Water Under 12～24 hours.
The centrifugal 10min when rotating speed is 15000r/min.
Dialyse in deionized water 48h with the bag filter that molecular cut off is 0.5～1kD.
The present invention adopts the N doping fluorescent carbon nano dot that high yield synthetic method obtains, by regulating and controlling amide containing unsaturated double-bond (or the carboxylic acid containing unsaturated double-bond or the long-chain fatty acid containing unsaturated double-bond) ratio, in regulation and control N doping fluorescent carbon nano dot, nitrogen content ranges for 5～10wt%.
Amino, carboxyl and hydroxyl are contained in the N doping fluorescent carbon nano dot surface that the inventive method prepares.Maximum excitation wavelength is at 330～370nm, and emission wavelength ranges is at 350～550nm.
The present invention with chitosan, for presoma, hydrothermal carbonization gets final product ultra-high yield (90%) synthetic nitrogen doping fluorescent carbon nano dot to amide containing unsaturated double-bond (or the carboxylic acid containing unsaturated double-bond or the long-chain fatty acid containing unsaturated double-bond).
Chitosan used by the present invention, the amide containing unsaturated double-bond (or the carboxylic acid containing unsaturated double-bond or the long-chain fatty acid containing unsaturated double-bond) low in raw material price, effectively reducing the production cost of fluorescent carbon nano dot, ultra-high yield (90%) synthesis is advantageously implemented synthesis magnanimity.To chitosan and amide containing unsaturated double-bond (or the carboxylic acid containing unsaturated double-bond or the long-chain fatty acid containing unsaturated double-bond) Direct Hydrothermal carbonization, step is simple, and synthetic yield is high, and without follow-up Passivation Treatment, is therefore suitable for industrial scale and produces.
Accompanying drawing explanation
Fig. 1 is the fluorescent carbon nano dot solid of the embodiment of the present invention 1 synthesis photo under ultra violet lamp；
Fig. 2 is the uv-visible absorption spectra figure of the fluorescent carbon nano dot of the embodiment of the present invention 1 synthesis；
Fig. 3 is the fluorescent carbon nano dot of the embodiment of the present invention 1 synthesis fluorescence emission spectrogram under different excitation wavelengths, 1 250nm in Fig. 3,2 270nm, 3 290nm, 4 310nm, 5 330nm, 6 350nm, 7 360nm, 8 370nm, 9 380nm, 10 400nm, 11 420nm, 12 440nm, 13 460nm, 14 480nm, 15 500nm；
Fig. 4 is the fluorescence lifetime fitted figure of the fluorescent carbon nano dot of the embodiment of the present invention 1 synthesis.
Detailed description of the invention
Embodiment 1: in the present embodiment, a kind of method of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot is completed by following step:
The acrylamide of 0.4g chitosan Yu 1.6g is dissolved in the ultra-pure water of 20mL, is configured to the mixed solution that concentration is 100mg/mL, above-mentioned mixed solution is placed in reaction in still, reacts 12 hours at 220 DEG C of hydrothermal carbonizations.Above-mentioned reactant liquor is 15000r/min centrifugal 10 minutes at rotating speed, remove a small amount of black precipitate composition granule in reactant liquor, dialyse in deionized water 48 hours with the dialyzer that molecular cut off is 0.5～1kD, obtain brownish black fluorescent carbon nanodot solution, lyophilization obtains N doping fluorescent carbon nano dot solid and is about 1.6g, and synthetic yield is about 80%.
Fig. 1 is the fluorescent carbon nano dot solid of the present embodiment synthesis photo under uviol lamp, and under 360nm uviol lamp, the N doping fluorescent carbon nano dot that quality is 1.6g presents bright yellow fluorescence.Fig. 2 is the uv-visible absorption spectra figure of the fluorescent carbon nanodot solution of the present embodiment synthesis, has an absworption peak near 241nm, it was shown that containing π-π double bond in fluorescent carbon nano dot structure.Fig. 3 is the fluorescent carbon aqueous nanodot solutions of the present embodiment synthesis fluorescence emission spectrogram under different excitation wavelengths, and fluorescence emission peak wavelength increases and red shift gradually with excitation wavelength, has the strongest emission peak under 370nm excitation wavelength.Fig. 4 is the fluorescence lifetime figure of the fluorescent carbon aqueous nanodot solutions of the present embodiment synthesis, finds that through the Fitting Calculation the fluorescence lifetime of this carbon nano dot is 4.85nm.
Embodiment 2: in the present embodiment, a kind of method of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot is completed by following step:
The maleic anhydride of 0.5g chitosan Yu 1.5g is dissolved in the ultra-pure water of 20mL, is configured to the mixed solution that concentration is 100mg/mL, above-mentioned mixed solution is placed in reaction in still, reacts 12 hours at 220 DEG C of hydrothermal carbonizations.Above-mentioned reactant liquor is 15000r/min centrifugal 10 minutes at rotating speed, remove a small amount of black precipitate composition granule in reactant liquor, dialyse in deionized water 48 hours with the dialyzer that molecular cut off is 0.5～1kD, obtain brown color fluorescent carbon nanodot solution, lyophilization obtains N doping fluorescent carbon nano dot solid, and synthetic yield is about 70%.
Embodiment 3: in the present embodiment, a kind of method of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot is completed by following step:
The N-DMAA of 0.2g chitosan Yu 3g is dissolved in the ultra-pure water of 20mL, is configured to the mixed solution that concentration is 160mg/mL, above-mentioned mixed solution is placed in reaction in still, reacts 24 hours at 180 DEG C of hydrothermal carbonizations.Above-mentioned reactant liquor is 15000r/min centrifugal 10 minutes at rotating speed, remove a small amount of black precipitate composition granule in reactant liquor, dialyse in deionized water 48 hours with the dialyzer that molecular cut off is 0.5～1kD, obtain brown color fluorescent carbon nanodot solution, lyophilization obtains N doping fluorescent carbon nano dot solid, and synthetic yield is about 75%.
Embodiment 4: in the present embodiment, a kind of method of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot is completed by following step:
The linoleic acid of 0.2g chitosan Yu 4g is placed in the ultra-pure water of 20mL, is configured to the mixed solution that concentration is 210mg/mL, above-mentioned mixed solution is placed in reaction in still, reacts 24 hours at 200 DEG C of hydrothermal carbonizations.Above-mentioned reactant liquor is 15000r/min centrifugal 10 minutes at rotating speed, remove a small amount of black precipitate composition granule in reactant liquor, dialyse in deionized water 48 hours with the dialyzer that molecular cut off is 0.5～1kD, obtain brown color fluorescent carbon nanodot solution, lyophilization obtains N doping fluorescent carbon nano dot solid, and synthetic yield is about 90%.
Claims (10)
1. the method for a ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot, it is characterized in that the synthetic method of N doping fluorescent carbon nano dot is completed by following step: be placed in ultra-pure water by chitosan with the amide containing unsaturated double-bond, sequentially pass through high speed centrifugation after carrying out hydrothermal carbonization again to separate, dialyse and frozen dried, N doping fluorescent carbon nano dot solid can be obtained.
2. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 1, it is characterised in that the mol ratio of described chitosan and the amide containing unsaturated double-bond is 0.01～1:1.
3. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 2, it is characterised in that the described amide containing unsaturated double-bond is a kind of or wherein several combination in N-DMAA, NIPA, acrylamide and n-methylolacrylamide.
4. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 2, it is characterised in that adopt the carboxylic acid containing unsaturated double-bond or the long-chain fatty acid containing unsaturated double-bond to replace the amide containing unsaturated double-bond.
5. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 4, it is characterized in that the described carboxylic acid containing unsaturated double-bond includes .beta.-methylacrylic acid, acrylic acid, methacrylic acid, cinnamic acid, a kind of or wherein several combination in acrylic acid methyl ester., fumaric acid, maleic anhydride and maleic acid.
6. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 4, it is characterised in that the described long-chain fatty acid containing unsaturated double-bond is a kind of or wherein several combination in linolenic acid, linoleic acid, sad, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid.
7. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 1, it is characterised in that described chitosan and the gross mass of amide containing unsaturated double-bond are 60～210mg:1mL with the volume ratio of water.
8. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 1, it is characterised in that 180～220 DEG C of hot carbonizations of Water Under 12～24 hours.
9. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 1, it is characterised in that the centrifugal 10min when rotating speed 15000r/min.
10. the method for a kind of ultra-high yield synthetic nitrogen doping fluorescent carbon nano dot according to claim 1, it is characterised in that dialyse in deionized water 48h with the bag filter that molecular cut off is 0.5～1kD.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106833629A (en) * | 2017-01-05 | 2017-06-13 | 东南大学 | A kind of Mitochondrially targeted fluorescent carbon point and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103361047A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院大连化学物理研究所 | Functional fluorescence carbon nanoparticles based on natural saccharide materials and preparation method and application thereof |
| CN104031642A (en) * | 2014-06-24 | 2014-09-10 | 山西大学 | Fluorescence carbon quantum dots, and preparation method and application thereof |
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| CN103361047A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院大连化学物理研究所 | Functional fluorescence carbon nanoparticles based on natural saccharide materials and preparation method and application thereof |
| CN104031642A (en) * | 2014-06-24 | 2014-09-10 | 山西大学 | Fluorescence carbon quantum dots, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
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| BAOQIANG LI ET AL.: "Hydrosoluble, UV-crosslinkable and injectable chitosan for patterned cell-laden microgel and rapid transdermal curing hydrogel in vivo", 《ACTA BIOMATERIALIA》 * |
| LEI WANG ET AL.: "High-yield synthesis of strong photoluminescent N-doped carbon nanodots derived from hydrosoluble chitosan for mercury ion sensing via smartphone APP", 《BIOSENSORS AND BIOELECTRONICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833629A (en) * | 2017-01-05 | 2017-06-13 | 东南大学 | A kind of Mitochondrially targeted fluorescent carbon point and its preparation method and application |
| CN106833629B (en) * | 2017-01-05 | 2019-05-31 | 东南大学 | A kind of Mitochondrially targeted fluorescent carbon point and its preparation method and application |
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