CN106672941A - Preparation and separation method of magnetic nanometer fluorescent carbon dot - Google Patents
Preparation and separation method of magnetic nanometer fluorescent carbon dot Download PDFInfo
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- CN106672941A CN106672941A CN201611228548.7A CN201611228548A CN106672941A CN 106672941 A CN106672941 A CN 106672941A CN 201611228548 A CN201611228548 A CN 201611228548A CN 106672941 A CN106672941 A CN 106672941A
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Abstract
The invention provides a preparation and separation method of magnetic nanometer fluorescent carbon dot, and belongs to the technical fields of new energy sources and new materials. The preparation and separation method is characterized in that crab shells of dining leftovers are used as a starting raw material of carbon dot synthesis; metal chloride salt is used as a catalyst and a passivating agent; a fluorescent carbon dot (2 to 5nm) with a nanometer magnetic nucleus is prepared by a 'one-pot' method under the hydrothermal condition; the obtained magnetic nanometer fluorescent carbon dot has magnetism and rich surface function groups, and is favorable for the modifying of carbon dot products, so as to obtain new application in different fields. The preparation and separation method has the advantages that a novel double-water phase extraction technique is applied to separate and purify the magnetic nanometer fluorescent carbon dot; the technology is simple, the separation effect is good, and a new method is provided for the separation of fluorescent carbon dots.
Description
Technical field
The invention belongs to new forms of energy and new material technology field, are related to a kind of preparation of magnetic Nano fluorescent carbon point and divide
From method.
Background technology
Fluorescent carbon quantum dot not only has as conventional semiconductors quantum dot and the new replacement fluorescent material of metal quantum point
The characteristics of having bioaffinity, fluorescent stability height and good chemical stability, and size and surface chemical property are controllable, are expected to
Replace traditional quantum dot in the application in the fields such as biomedical and biochemical analysis and detection.
The synthetic method of fluorescent carbon quantum dot is more, there is chemical oxidization method (201410260854.3), laser ablation, electricity
Chemical method (CN201210408835.1), microwave assisting method (CN201510147559.1), pyrolysis synthetic method
(CN201010126320.3), ultrasonic (CN201410399540.1), hydrothermal synthesis method
(CN201410504664.1) etc..Wherein in hydrothermal synthesis method, water works as a kind of chemical constituent and participates in reaction,
One pack system tiny crystals can be prepared, with particle diameter little (nanoscale), purity height, good dispersion, uniform, narrowly distributing, soilless sticking, shape
Shape is controllable and beneficial to the features such as the depollution of environment, is widely used in nano material synthesis with preparation.But Hydrothermal Synthesiss
Method prepares carbon point and yet suffers from some drawbacks and deficiency, and for example with hydrothermal synthesis method the carbon point aqueous solution is prepared, and needs mostly
Jing filtrations, dialysis, freeze-drying etc. process and carbon point are purified, and post processing is complicated, and treating capacity is low, is unfavorable for the expansion of carbon point
Production.
The content of the invention
During the present invention is in order to solve prior art, fluorescence quantum low yield, fluorescence that Hydrothermal Synthesiss carbon point methods are present
The problems such as intensity is on the weak side, fluorescence lifetime is short and post processing is complicated, there is provided a kind of preparation of magnetic Nano fluorescent carbon point with separate
Method.The present invention by the use of natural nitrogen containing polymer material chitin and chitosan as the raw material of carbon point, with FeCl3、NiCl2
And CoCl2Deng as catalyst and passivator, Jing hydro-thermal reactions acquisition magnetic Nano fluorescent carbon quantum dot.Afterwards using new double
Water phase extraction system, realizes the isolation and purification of magnetic Nano fluorescent carbon quantum dot.Obtained magnetic Nano fluorescent carbon quantum dot
Abundant functional group is contained on surface, such as-OH ,-COOH ,-NH2Deng the potentiality with further functionalization.
The present invention proposes a kind of preparation of magnetic Nano fluorescent carbon point and detached concrete technical scheme, including following step
Suddenly：
The first step, weighs the chitin or shitosan of certain mass, and with metal chloride, deionized water 1 is pressed:0.1~0.5:
50~100 mass ratio mixing, 2~8h of hydro-thermal reaction at 180 DEG C~220 DEG C obtains brown color magnetic Nano fluorescent carbon
The thick liquid of point.
Second step, by the thick liquid of magnetic Nano fluorescent carbon point and organic solvent, inorganic salts 1 is pressed:0.2~1:1~2 mass ratio
Example mixing, mixes at a certain temperature, split-phase after standing a period of time, and upper phase is containing the organic molten of magnetic Nano fluorescent carbon point
Agent, lower phase is the mixed aqueous solution of metal chloride and inorganic salts；Upper strata organic solvent phase is collected, organic solvent is reclaimed, gained is shallow
Yellow solid is the magnetic Nano fluorescent carbon point after isolating and purifying.The step introduces " hydrophilic organic solvent-inorganic salts " double water
Phase extraction system, realizes magnetic Nano fluorescent carbon point and FeCl3、NiCl2And CoCl2Deng slaine it is quick, efficiently separate,
Significantly reduce the cost of separation-extraction technology.
Above-mentioned metal chloride is NiCl2、FeCl3Or CoCl2In one kind.With FeCl3、NiCl2And CoCl2Deng as catalysis
Agent and passivator, while promoting to improve nanoscale fluorescent carbon point, can directly obtain under hydrothermal conditions fluorescent carbon point parcel
Nanometer magnetic core, so as to obtain the magnetic Nano fluorescent carbon point of uniform particle sizes (2~5nm).
Above-mentioned organic solvent is the one kind in ethanol, propyl alcohol or acetone.
Above-mentioned inorganic salts are dipotassium hydrogen phosphate or potassium carbonate.
The mixing temperature of above-mentioned second step is 22~25 DEG C, and time of repose is 15~30min after mixing.
Chitin or shitosan in the above-mentioned first step, from crab shell.
The invention has the beneficial effects as follows, magnetic Nano fluorescent carbon point is prepared for raw material using remaining meal rubbish crab shell, it is capable of achieving
The recycling of abandoned biomass.While environmental pollution is reduced, there is provided new ecomaterial.Using metal chloride as urging
Agent and passivator, Jing hydro-thermal method synthesizing magnetic nano fluorescent carbon points, carbon point yield is up to 60%, and fluorescence quantum yield is reachable
21%.Gained magnetic Nano fluorescent carbon point not only has magnetic, and has abundant surface functional group, is conducive to carbon point product
It is modified, so as to obtain new application in different field.New aqueous two phase extraction technique is used for magnetic Nano fluorescent carbon by the present invention
That what is put isolates and purifies, and process is simple, good separating effect, the separation for fluorescent carbon point provides a kind of new method.
Description of the drawings
Fig. 1 is the TEM spectrograms of nano fluorescent carbon point.
Specific embodiment
Technical scheme is described in detail below in conjunction with specific embodiment and accompanying drawing.
Embodiment one
Remaining meal rubbish crab shell is cleaned, removal of impurities, drying, be crushed to 0.1mm, remove the impurity such as calcium carbonate and protein, obtain
Obtain thick chitin.The dried chitins of 1g are weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reactions
8h, obtains the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 55%, and fluorescence quantum yield is up to 19%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates mixes with 5g ethanol, after mixing at 22 DEG C
Stand 15min split-phases, NiCl2Clearance is up to 99%.Phase in collection, reclaims ethanol, obtains magnetic Nano fluorescent carbon point product
Yield is up to 93%.The TEM spectrograms of nano fluorescent carbon point are as shown in Figure 1.
Embodiment two
Discarded river crab crab shell is cleaned, removal of impurities, drying, be crushed to 0.1mm, remove the impurity such as calcium carbonate and protein,
Obtain thick shitosan.The dried shitosans of 1g are weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reactions
8h, obtains the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 60%, and fluorescence quantum yield is up to 21%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates mixes with 5g ethanol, after mixing at 22 DEG C
Stand 20min split-phases, NiCl2Clearance is up to 99%.Phase in collection, reclaims ethanol, obtains magnetic Nano fluorescent carbon point product
Yield is up to 95%.
Embodiment three
The dried shitosans of 1g are weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reactions 2h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 51%, and fluorescence quantum yield is up to 19%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates mixes with 5g propyl alcohol, after mixing at 22 DEG C
Stand 15min split-phases, NiCl2Clearance is up to 99%.Phase in collection, reclaims propyl alcohol, obtains magnetic Nano fluorescent carbon point product
Yield is 87%.
Example IV
The dried shitosans of 1g are weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reactions 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 56%, and fluorescence quantum yield is up to 20%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g potassium carbonate mixes with 5g acetone, stand after mixing at 22 DEG C
15min split-phases, NiCl2Clearance is up to 99%.Phase in collection, reclaims acetone, obtains the yield of magnetic Nano fluorescent carbon point product
For 82%.
Embodiment five
The dried chitins of 1g are weighed, with 0.1gNiCl2, 100g deionized waters mixing, in 180 DEG C of hydro-thermal reactions 2h,
Obtain the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 30%, and fluorescence quantum yield is 15%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and 5g dipotassium hydrogen phosphates mix with 10g ethanol, it is quiet after mixing at 22 DEG C
Put 30min split-phases, NiCl2Clearance is up to 99%.Ethanol is reclaimed in phase in collection, Jing vacuum distillations, obtains magnetic Nano fluorescent carbon
The yield of point product is up to 98%.
Embodiment six
The dried shitosans of 1g are weighed, with 0.1gNiCl2, 50g deionized waters mixing, in 200 DEG C of hydro-thermal reactions 8h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 41%, and fluorescence quantum yield is 14.5%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates mix with 5g ethanol, stand after mixing at 25 DEG C
15min split-phases, NiCl2Clearance is up to 99%.Phase in collection, reclaims ethanol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 95%.
Embodiment seven
The dried shitosans of 1g are weighed, with 0.2gFeCl3, 80g deionized waters mixing, in 200 DEG C of hydro-thermal reactions 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 30%, and fluorescence quantum yield is 1%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates mix with 5g ethanol, stand after mixing at 25 DEG C
30min split-phases, FeCl3Clearance is up to 99%.Phase in collection, reclaims ethanol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 93%.
Embodiment eight
The dried shitosans of 1g are weighed, with 0.2gCoCl2, 80g deionized waters mixing, in 200 DEG C of hydro-thermal reactions 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon point yield is 24%, and fluorescence quantum yield is 10%.
Weigh the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates mix with 5g ethanol, stand after mixing at 22 DEG C
30min split-phases, CoCl2Clearance is up to 99%.Phase in collection, reclaims ethanol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 90%.
Claims (10)
1. a kind of preparation of magnetic Nano fluorescent carbon point and separation method, it is characterised in that comprise the following steps：
The first step, weighs the chitin or shitosan of certain mass, and with metal chloride, deionized water 1 is pressed:0.1~0.5:50~
100 mass ratio mixing, 2~8h of hydro-thermal reaction at 180 DEG C~220 DEG C obtains brown color magnetic Nano fluorescent carbon point thick
Liquid；
Second step, by the thick liquid of magnetic Nano fluorescent carbon point and organic solvent, inorganic salts 1 is pressed:0.2~1:1~2 mass ratio is mixed
Close, mix at a certain temperature, split-phase after standing a period of time collects upper strata organic solvent phase, reclaim organic solvent, it is remaining shallow
Yellow solid is the magnetic Nano fluorescent carbon point after isolating and purifying.
2. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 1 and separation method, it is characterised in that metal
Villaumite is NiCl2、FeCl3Or CoCl2In one kind.
3. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 1 and 2 and separation method, it is characterised in that
Organic solvent is the one kind in ethanol, propyl alcohol or acetone.
4. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 1 and 2 and separation method, it is characterised in that
Inorganic salts are dipotassium hydrogen phosphate or potassium carbonate.
5. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 3 and separation method, it is characterised in that inorganic
Salt is dipotassium hydrogen phosphate or potassium carbonate.
6. a kind of preparation of the magnetic Nano fluorescent carbon point according to claim 1 or 2 or 5 and separation method, its feature exists
In the mixing temperature of second step is 22~25 DEG C, and time of repose is 15~30min after mixing.
7. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 3 and separation method, it is characterised in that second
The mixing temperature of step is 22~25 DEG C, and time of repose is 15~30min after mixing.
8. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 4 and separation method, it is characterised in that second
The mixing temperature of step is 22~25 DEG C, and time of repose is 15~30min after mixing.
9. a kind of preparation of the magnetic Nano fluorescent carbon point according to claim 1 or 2 or 5 and separation method, its feature exists
In the chitin or shitosan in the first step, from crab shell.
10. a kind of preparation of magnetic Nano fluorescent carbon point according to claim 3 and separation method, it is characterised in that
Chitin or shitosan in one step, from crab shell.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604011A (en) * | 2017-11-06 | 2018-01-19 | 中国石油大学(北京) | A kind of method for improving anaerobic fermentation gas production as accelerator using carbon quantum dot |
| CN109652065A (en) * | 2018-11-30 | 2019-04-19 | 安康德美（中山）纳米科技有限公司 | A kind of preparation method of gold doping fluorescent carbon quantum dot |
| CN112592717A (en) * | 2020-12-18 | 2021-04-02 | 湖南工业大学 | Nano fluorescent carbon dots and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090009469A1 (en) * | 2007-07-06 | 2009-01-08 | Microsoft Corporation | Multi-Axis Motion-Based Remote Control |
| US20110158901A1 (en) * | 2009-12-29 | 2011-06-30 | Swadeshmukul Santra | Chitosan-based nanoparticles and methods for making and using the same |
| CN102849724A (en) * | 2012-10-12 | 2013-01-02 | 上海交通大学 | Preparation method of water-soluble carbon quantum dots |
| CN103466600A (en) * | 2013-09-26 | 2013-12-25 | 沈阳大学 | Preparation method of environment-friendly low-toxic fluorescent carbon nano particle liquor |
| CN105505387A (en) * | 2014-09-26 | 2016-04-20 | 西南大学 | Fluorescence carbon nanometer quantum dot based on natural pectin and preparation method thereof |
-
2016
- 2016-12-27 CN CN201611228548.7A patent/CN106672941B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090009469A1 (en) * | 2007-07-06 | 2009-01-08 | Microsoft Corporation | Multi-Axis Motion-Based Remote Control |
| US20110158901A1 (en) * | 2009-12-29 | 2011-06-30 | Swadeshmukul Santra | Chitosan-based nanoparticles and methods for making and using the same |
| CN102849724A (en) * | 2012-10-12 | 2013-01-02 | 上海交通大学 | Preparation method of water-soluble carbon quantum dots |
| CN103466600A (en) * | 2013-09-26 | 2013-12-25 | 沈阳大学 | Preparation method of environment-friendly low-toxic fluorescent carbon nano particle liquor |
| CN105505387A (en) * | 2014-09-26 | 2016-04-20 | 西南大学 | Fluorescence carbon nanometer quantum dot based on natural pectin and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604011A (en) * | 2017-11-06 | 2018-01-19 | 中国石油大学(北京) | A kind of method for improving anaerobic fermentation gas production as accelerator using carbon quantum dot |
| CN107604011B (en) * | 2017-11-06 | 2020-07-31 | 中国石油大学(北京) | Method for improving anaerobic fermentation gas production by using carbon quantum dots as accelerant |
| CN109652065A (en) * | 2018-11-30 | 2019-04-19 | 安康德美（中山）纳米科技有限公司 | A kind of preparation method of gold doping fluorescent carbon quantum dot |
| CN109652065B (en) * | 2018-11-30 | 2021-08-20 | 安康德美（中山）纳米科技有限公司 | Preparation method of gold-doped fluorescent carbon quantum dots |
| CN112592717A (en) * | 2020-12-18 | 2021-04-02 | 湖南工业大学 | Nano fluorescent carbon dots and preparation method thereof |
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