CN109111919A - A kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products - Google Patents
A kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products Download PDFInfo
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- CN109111919A CN109111919A CN201811155859.4A CN201811155859A CN109111919A CN 109111919 A CN109111919 A CN 109111919A CN 201811155859 A CN201811155859 A CN 201811155859A CN 109111919 A CN109111919 A CN 109111919A
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Abstract
The invention discloses a kind of preparation methods of the manganese ion doping carbon quantum dot of complete water-soluble products.Its preparation step is: first respectively dissolving divalent manganesetion compound and EDETATE SODIUM salt in deionized water；Chelatropic reaction is sufficiently stirred again；By the solution low-temperature evaporation crystallization after reaction；Crystal is placed in nitrogen atmosphere in certain temperature and heats carbonization treatment in certain time again；Solid carbide is finally dissolved in deionized water, obtains complete water-soluble products, is purified by dialysis, obtains manganese ion doping carbon quantum dot.The invention has the advantages that: compared with the carbon quantum dot of the undoped or Copper-cladding Aluminum Bar of other thermal decomposition methods preparation or N doping or copper N doping, the carbide solid that the method for the present invention obtains is completely soluble, there is no solid residue, by-product and intermediate product are few, without subsequent grinding, sonic oscillation and centrifugal treating step.Operation of the present invention is simple, and repeatability is strong, and fluorescence quantum yield is higher, and stability is good, and raw material is cheap, is suitable for large-scale mass production.
Description
Technical field
The present invention relates to fluorescence display technical field of nano material, and in particular to a kind of manganese ion doping carbon quantum dot
Preparation method.
Background technique
Carbon quantum dot is a kind of novel carbon-based zero dimension material.The fluorescence lifetime of carbon quantum dot is long, fluorescence property is stablized, also
Have many advantages, such as that good water solubility, hypotoxicity, environmental-friendly, raw material sources are wide, at low cost, biocompatibility is preferable.Carbon amounts
Son point is widely used, in many fields such as medical imaging technology, environmental monitoring, chemical analysis, catalyst preparation, energy development
There is good application prospect.The preparation method of carbon quantum dot is also very much, including arc discharge method, laser corrode method, electrochemistry
Synthetic method, chemical oxidization method, combustion method, hydrothermal synthesis method, microwave process for synthesizing, template etc..Wherein equipment needed for thermal decomposition method
Less, operating process is simple,
Currently, the preparation method of manganese ion doping carbon quantum dot is less.The method of existing document is solvent-thermal method, selection
Raw material be manganous chloride and citric acid, product be tetravalence additive Mn carbon quantum dot.Part manganese is not in the carbonation reaction
It can be substantially oxidized, it is less reproducible, it is difficult to accomplish to be mass produced.
Summary of the invention
The invention proposes a kind of new preparation process of the manganese ion doping carbon quantum dot of new complete water-soluble products, should
Method uses the water-soluble manganese ion compound of divalent as manganese source, then with disodium edta (EDETATE SODIUM salt) to manganese
Ion makees chelatropic reaction, and for chelate after low temperature drying and nitrogen atmosphere thermal decomposition, solid product can be directly dissolved in water, obtain
The manganese ion doping carbon quantum dot of complete water-soluble products, by-product and intermediate product are few, are not necessarily to sonic oscillation and centrifugation step,
Preparation process is greatly simplified, energy conservation and environmental protection requirement is met.It gets a promotion in terms of fluorescent stability, and preparation process repeatability is more
By force, easy to operate, required material rate is flexibly controllable.
The chelatropic reaction, it is related to the temperature of reaction solution and pH value, it is anti-in chelating of the EDETATE SODIUM salt to manganese ion
Ying Zhong, room temperature range and pH value can sufficiently carry out chelatropic reaction 4~9.
The invention is realized in this way.A kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products,
It the steps include:
A) divalent manganesetion compound and disodium edta (EDETATE SODIUM salt) are first pressed into manganese ion and EDETATE SODIUM salt
Molar ratio 1:1~1:10 weigh, dissolve, then be sufficiently mixed carry out chelatropic reaction, obtain colourless in deionized water respectively
The solution of clear；
B) the transparent solution of achromaticity and clarification described in step a is subjected to low-temperature evaporation crystallization；
C) crystallized product is placed in nitrogen atmosphere again and is heated, 250 DEG C~450 DEG C of temperature, time 0.5h~3h, heating speed
5 DEG C/min of rate carries out carbonization treatment, then cools to room temperature；
D) solid carbide that finally will be cooled to room temperature is dissolved in deionized water, complete water-soluble products is obtained, by saturating
Analysis purification, obtains manganese ion doping carbon quantum dot；
The divalent manganesetion compound is to be soluble in aqueous manganese acetate, manganese chloride, manganese sulfate, and EDETATE SODIUM salt is second two
Amine tetraacethyl disodium, tetrasodium ethylenediamine tetraacetate.
The ratio of the divalent manganesetion compound and EDETATE SODIUM salt is adjustable, can obtain different manganese ions by adjusting ratio
The carbon quantum dot of doping, illumination effect are also different.
The manganese ion doping carbon quantum dot of the complete water-soluble products refers to the solid powder obtained after thermal decomposition
Object is fully soluble in deionized water, obtains the quantum dot solution of clear, insoluble without macroscopic precipitating or suspension etc.
Object.
Manganese ion doping carbon quantum dot prepared by the present invention, fluorescence quantum yield is high, and has preferable thermal stability.
The carbon quantum dot of undoped or Copper-cladding Aluminum Bar known to the method for the present invention and current document or N doping or additive Mn
Preparation method is compared, and the carbide that the present invention obtains is completely soluble, not the solid residue of insoluble in water, is not necessarily to subsequent ultrasound
Oscillation and centrifugal treating step.Easy to operate, repeatability is strong, and fluorescence quantum yield is higher, and stability is good, and raw material is cheap, is suitble to
Large-scale serial production.
The present invention applies in medical imaging technology, environmental monitoring, chemical analysis.
Detailed description of the invention
Fig. 1 is that molar ratio is 1:1 in embodiment 1, and thermal decomposition temperature is the glimmering of 325 DEG C of gained manganese ion doping carbon quantum dots
Optical emission spectroscopy figure.
Fig. 2 is that molar ratio is 1:1 in embodiment 1, and thermal decomposition temperature is the glimmering of 375 DEG C of gained manganese ion doping carbon quantum dots
Optical emission spectroscopy figure.
Fig. 3 is that molar ratio is 1:3 in embodiment 2, and thermal decomposition temperature is the glimmering of 325 DEG C of gained manganese ion doping carbon quantum dots
Optical emission spectroscopy figure.
Fig. 4 is that molar ratio is 1:5 in embodiment 3, and thermal decomposition temperature is the glimmering of 400 DEG C of gained manganese ion doping carbon quantum dots
Optical emission spectroscopy figure.
Specific embodiment
Embodiment 1:
1. weighing 1mmol manganese acetate and 1mmol disodium ethylene diamine tetraacetate respectively, dissolve in deionized water.Again sufficiently
Stirring carries out chelatropic reaction, obtains the transparent solution of achromaticity and clarification, and solution is carried out low-temperature evaporation drying, obtains white to colourless
Solid dried object.
2. the dried object of step 1. is placed in nitrogen atmosphere again, 5 DEG C/min of heating rate, respectively in 325 DEG C and 375 DEG C
Temperature 2h carries out carbonization treatment；The carbide that finally will be cooled to room temperature is dissolved in deionized water, obtains completely water-soluble produce
Object purifies by dialysis, obtains manganese ion doping carbon quantum dot.
Manganese ion doping carbon quantum dot manufactured in the present embodiment, in 340~500nm of excitation wavelength, the model of fluorescence peak
Enclose is 425~550nm (325 DEG C of thermal decomposition temperature) and 468~568nm (375 DEG C of thermal decomposition temperature) respectively.
Embodiment 2:
1. weighing 1mmol manganese acetate and 3mmol disodium ethylene diamine tetraacetate respectively, dissolve in deionized water.Again sufficiently
Stirring carries out chelatropic reaction, obtains the transparent solution of achromaticity and clarification, and solution is carried out low-temperature evaporation drying, obtains white to colourless
Solid dried object.
2. the dried object of step 1. is placed in nitrogen atmosphere again, 5 DEG C/min of heating rate, in 325 DEG C of temperature 2h,
Carry out carbonization treatment；The carbide that finally will be cooled to room temperature is dissolved in deionized water, obtains complete water-soluble products, by dialysis
Purification, obtains manganese ion doping carbon quantum dot.
Manganese ion doping carbon quantum dot manufactured in the present embodiment, in 340~500nm of excitation wavelength, the model of fluorescence peak
Enclosing is 428~548nm.
Embodiment 3:
1. weighing 1mmol manganese acetate and 5mmol tetrasodium ethylenediamine tetraacetate respectively, dissolve in deionized water.Again sufficiently
Stirring carries out chelatropic reaction, obtains the transparent solution of achromaticity and clarification, and solution is carried out low-temperature evaporation drying, obtains white to colourless
Solid dried object.
2. the dried object of step 1. is placed in nitrogen atmosphere again, 5 DEG C/min of heating rate, in 400 DEG C of temperature 2h,
Carry out carbonization treatment；The carbide that finally will be cooled to room temperature is dissolved in deionized water, obtains complete water-soluble products, by dialysis
Purification, obtains manganese ion doping carbon quantum dot.
Manganese ion doping carbon quantum dot manufactured in the present embodiment, in 340~500nm of excitation wavelength, the model of fluorescence peak
Enclosing is 465~555nm.
Claims (4)
1. a kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products, it is characterised in that including following step
It is rapid:
A) first the rubbing by manganese ion and EDETATE SODIUM salt by divalent manganesetion compound and disodium edta (EDETATE SODIUM salt)
Your ratio 1:1~1:10 is weighed, and is dissolved, then be sufficiently mixed carry out chelatropic reaction in deionized water respectively, is obtained achromaticity and clarification
Transparent solution；
B) the transparent solution of achromaticity and clarification described in step a is subjected to low-temperature evaporation crystallization；
C) crystallized product is placed in nitrogen atmosphere again and is heated, 250 DEG C~450 DEG C of temperature, time 0.5h~3h, heating rate 5
DEG C/min, carbonization treatment is carried out, is then cooled to room temperature；
D) solid carbide that finally will be cooled to room temperature is dissolved in deionized water, obtains complete water-soluble products, mentions by dialysis
It is pure, obtain manganese ion doping carbon quantum dot；
The divalent manganesetion compound is to be soluble in aqueous manganese acetate, manganese chloride, manganese sulfate, and EDETATE SODIUM salt is ethylenediamine tetraacetic
Acetic acid disodium, tetrasodium ethylenediamine tetraacetate.
2. a kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products according to claim 1,
It is characterized in that the ratio of divalent manganesetion compound and EDETATE SODIUM salt is adjustable, different manganese ion dopings can be obtained by adjusting ratio
The carbon quantum dot of amount, illumination effect are also different.
3. a kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products according to claim 1,
Product after being characterized in that hot carbonization treatment has completely water-soluble, no solid residue.
4. a kind of preparation method of the manganese ion doping carbon quantum dot of complete water-soluble products according to claim 1,
It is characterized in that applying in medical imaging technology, environmental monitoring, chemical analysis.
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Cited By (2)
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| CN114410299A (en) * | 2022-01-27 | 2022-04-29 | 郑州大学 | Carbon dot and preparation method of carbon dot-based composite material |
| CN115433570A (en) * | 2022-09-27 | 2022-12-06 | 天津师范大学 | Novel near-infrared fluorescence-magnetic manganese quantum dot probe and synthetic method and application thereof |
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| CN115433570A (en) * | 2022-09-27 | 2022-12-06 | 天津师范大学 | Novel near-infrared fluorescence-magnetic manganese quantum dot probe and synthetic method and application thereof |
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