CN106672941B - A kind of preparation of magnetic Nano fluorescent carbon point and separation method - Google Patents
A kind of preparation of magnetic Nano fluorescent carbon point and separation method Download PDFInfo
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- CN106672941B CN106672941B CN201611228548.7A CN201611228548A CN106672941B CN 106672941 B CN106672941 B CN 106672941B CN 201611228548 A CN201611228548 A CN 201611228548A CN 106672941 B CN106672941 B CN 106672941B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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Abstract
The invention belongs to new energy and new material technology field.The starting material for selecting remaining meal rubbish crab shell to be synthesized as carbon dots, using metal chloride as catalyst and passivator, " one kettle way " prepares the fluorescent carbon point (2~5nm) with nanometer magnetic core under hydrothermal conditions.Gained magnetic Nano fluorescent carbon point not only has magnetism, but also has abundant surface functional group, is conducive to the modification of carbon dots product, to obtain new application in different field.The present invention also the isolating and purifying for magnetic Nano fluorescent carbon point by novel aqueous two phase extraction technique, simple for process, good separating effect provides a kind of new method for the separation of fluorescent carbon point.
Description
Technical field
The invention belongs to new energy and new material technology field, be related to a kind of preparation of magnetic Nano fluorescent carbon point with point
From method.
Background technology
Novel replacement fluorescent material of the fluorescent carbon quantum dot as conventional semiconductors quantum dot and metal quantum point, not only has
Have the characteristics that bioaffinity, fluorescent stability are high and chemical stability is good, and size and surface chemical property are controllable, are expected to
Application of the traditional quantum dot of substitution in fields such as biomedical and biochemical analysis and detections.
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, there is grain size small (nanoscale), purity height, good dispersion, uniform, narrowly distributing, soilless sticking, shape
The features such as shape is controllable and is conducive to the depollution of environment is widely used in nano material synthesis with preparation.But hydrothermal synthesis
Method prepares carbon dots and still has some drawbacks and deficiency, prepares carbon dots aqueous solution for example, by using hydrothermal synthesis method, needs mostly
Carbon dots are purified through the processing such as filtering, dialysis, freeze-drying, post-processing is complicated, and treating capacity is low, is unfavorable for the expansion of carbon dots
Production.
Invention content
The present invention is in order to solve in the prior art, fluorescence quantum low yield, fluorescence existing for hydrothermal synthesis carbon dots method
The problems such as intensity is on the weak side, fluorescence lifetime is short and post-processing is complicated, provides a kind of preparation of magnetic Nano fluorescent carbon point and detaches
Method.The present invention is using natural nitrogen containing polymer material chitin and chitosan as the raw material of carbon dots, with FeCl3、NiCl2
And CoCl2Deng be used as catalyst and passivator, through hydro-thermal reaction obtain magnetic Nano fluorescent carbon quantum dot.It uses later novel 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 specific technical solution for preparing with detaching of magnetic Nano fluorescent carbon point, including following step
Suddenly：
The first step weighs the chitin or chitosan of certain mass, and 1 is pressed with metal chloride, deionized water:0.1~0.5:
50~100 mass ratio mixing, 2~8h of hydro-thermal reaction at 180 DEG C~220 DEG C obtain brown color magnetic Nano fluorescent carbon
The thick liquid of point.
The thick liquid of magnetic Nano fluorescent carbon point and organic solvent, inorganic salts are pressed 1 by second step:0.2~1:1~2 mass ratio
Example mixing, mixing, split-phase after standing a period of time, upper phase are the organic molten of the fluorescent carbon point containing magnetic Nano at a certain temperature
Agent, lower phase are the mixed aqueous solution of metal chloride and inorganic salts；Upper layer organic solvent phase is collected, organic solvent is recycled, 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 CoCl2Equal metal salts 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 fluorescent carbon point package under hydrothermal conditions
Nanometer magnetic core, to obtain the magnetic Nano fluorescent carbon point of uniform particle sizes (2~5nm).
Above-mentioned organic solvent is one kind in ethyl alcohol, 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 in the above-mentioned first step or chitosan derive from crab shell.
The invention has the advantages that using remaining meal rubbish crab shell be raw material prepare magnetic Nano fluorescent carbon point, it can be achieved that
The recycling of abandoned biomass.While reducing environmental pollution, new ecomaterial is provided.Using metal chloride as urging
Agent and passivator, through hydro-thermal method synthesizing magnetic nano fluorescent carbon dots, for carbon dots yield up to 60%, fluorescence quantum yield is reachable
21%.Gained magnetic Nano fluorescent carbon point not only has magnetism, but also has abundant surface functional group, is conducive to carbon dots product
It is modified, to obtain new application in different field.Novel aqueous two phase extraction technique is used for magnetic Nano fluorescent carbon by the present invention
Point isolates and purifies, and simple for process, good separating effect provides a kind of new method for the separation of fluorescent carbon point.
Description of the drawings
Fig. 1 is the TEM spectrograms of nano fluorescent carbon dots.
Specific implementation mode
Technical scheme of the present invention is described in detail below in conjunction with specific implementation mode and attached drawing.
Embodiment one
Remaining meal rubbish crab shell is cleaned, removal of impurities, is dried, 0.1mm is crushed to, removes the impurity such as calcium carbonate and protein, obtain
Obtain thick chitin.The chitin after 1g dryings is 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 dots yield is 55%, and fluorescence quantum yield is up to 19%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates is mixed with 5g ethyl alcohol, after 22 DEG C of mixings
Stand 15min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles ethyl alcohol, obtains magnetic Nano fluorescent carbon point product
Yield is up to 93%.The TEM spectrograms of nano fluorescent carbon dots are as shown in Figure 1.
Embodiment two
Discarded river crab crab shell is cleaned, removal of impurities, is dried, 0.1mm is crushed to, removes the impurity such as calcium carbonate and protein,
Obtain thick chitosan.The chitosan after 1g dryings is 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 dots yield is 60%, and fluorescence quantum yield is up to 21%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates is mixed with 5g ethyl alcohol, after 22 DEG C of mixings
Stand 20min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles ethyl alcohol, obtains magnetic Nano fluorescent carbon point product
Yield is up to 95%.
Embodiment three
The chitosan after 1g dryings is weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reaction 2h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 51%, and fluorescence quantum yield is up to 19%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and the dissolving of 1g dipotassium hydrogen phosphates is mixed with 5g propyl alcohol, after 22 DEG C of mixings
Stand 15min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles propyl alcohol, obtains magnetic Nano fluorescent carbon point product
Yield is 87%.
Example IV
The chitosan after 1g dryings is weighed, with 0.2gNiCl2, 80g deionized waters mixing, in 220 DEG C of hydro-thermal reaction 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 56%, and fluorescence quantum yield is up to 20%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g potassium carbonate is mixed with 5g acetone, stood after 22 DEG C of mixings
15min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles acetone, obtains the yield of magnetic Nano fluorescent carbon point product
It is 82%.
Embodiment five
The chitin after 1g dryings is weighed, with 0.1gNiCl2, the mixing of 100g deionized waters, in 180 DEG C of hydro-thermal reaction 2h,
Obtain the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 30%, and fluorescence quantum yield is 15%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and 5g dipotassium hydrogen phosphates is mixed with 10g ethyl alcohol, it is quiet after 22 DEG C of mixings
Set 30min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles ethyl alcohol through vacuum distillation, obtains magnetic Nano fluorescent carbon
The yield of point product is up to 98%.
Embodiment six
The chitosan after 1g dryings is weighed, with 0.1gNiCl2, 50g deionized waters mixing, in 200 DEG C of hydro-thermal reaction 8h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 41%, and fluorescence quantum yield is 14.5%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates is mixed with 5g ethyl alcohol, stood after 25 DEG C of mixings
15min split-phases, NiCl2Removal rate is up to 99%.Phase in collection recycles ethyl alcohol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 95%.
Embodiment seven
The chitosan after 1g dryings is weighed, with 0.2gFeCl3, 80g deionized waters mixing, in 200 DEG C of hydro-thermal reaction 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 30%, and fluorescence quantum yield is 1%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates is mixed with 5g ethyl alcohol, stood after 25 DEG C of mixings
30min split-phases, FeCl3Removal rate is up to 99%.Phase in collection recycles ethyl alcohol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 93%.
Embodiment eight
The chitosan after 1g dryings is weighed, with 0.2gCoCl2, 80g deionized waters mixing, in 200 DEG C of hydro-thermal reaction 4h, obtain
To the thick liquid of magnetic Nano fluorescent carbon point.Carbon dots yield is 24%, and fluorescence quantum yield is 10%.
It weighs the thick liquid of 5g magnetic Nano fluorescent carbon points and 1g dipotassium hydrogen phosphates is mixed with 5g ethyl alcohol, stood after 22 DEG C of mixings
30min split-phases, CoCl2Removal rate is up to 99%.Phase in collection recycles ethyl alcohol, obtains the yield of magnetic Nano fluorescent carbon point product
Up to 90%.
Claims (2)
1. preparation and the separation method of a kind of magnetic Nano fluorescent carbon point, it is characterised in that include the following steps：
The first step weighs the chitin or chitosan of certain mass, and 1 is pressed with metal chloride, deionized water:0.1~0.5:50~
It is thick to obtain brown color magnetic Nano fluorescent carbon point by 100 mass ratio mixing, 2~8h of hydro-thermal reaction at 180 DEG C~220 DEG C
Liquid；
The thick liquid of magnetic Nano fluorescent carbon point and organic solvent, inorganic salts are pressed 1 by second step:0.2~1:1~2 mass ratio is mixed
It closes, at a certain temperature mixing, split-phase after standing a period of time collects upper layer organic solvent phase, recycles organic solvent, remaining shallow
Yellow solid is the magnetic Nano fluorescent carbon point after isolating and purifying；
Metal chloride is NiCl2、FeCl3Or CoCl2In one kind；
Organic solvent is one kind in ethyl alcohol, propyl alcohol or acetone；
Inorganic salts are dipotassium hydrogen phosphate or potassium carbonate；
Chitin in the first step or chitosan derive from crab shell.
2. preparation and the separation method of a kind of magnetic Nano fluorescent carbon point according to claim 1, which is characterized in that second
The mixing temperature of step is 22~25 DEG C, and time of repose is 15~30min after mixing.
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| 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 |
| 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 |
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