CN105316697B - A kind of preparation method of solid-state carbon quantum dot - Google Patents
A kind of preparation method of solid-state carbon quantum dot Download PDFInfo
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Abstract
The invention belongs to carbon quantum dot material preparing technical field, it is related to a kind of preparation method of solid-state carbon quantum dot, first ionic liquid and nitriles substance is mixed as electrolyte and be put into electrolytic cell；It is put into electrolytic cell respectively as anode and negative electrode from two area platinum plate electrodes again, switching on power carries out reacting the light brown solution obtained doped with solid matter；Being then doped with the light brown solution of solid matter carries out suction filtration, and is transferred in clean container ware after the solid matter vacuum drying that suction filtration is obtained and obtains solid carbon quantum dot；Its preparation process is simple, and easy to operate, principle is easy to get, low cost, the solid-state carbon quantum dot good water solubility of preparation, photoluminescent property stabilization, it is easy to storage and transport.
Description
Technical field：
The invention belongs to carbon quantum dot material preparing technical field, it is related to a kind of electricity based on non-carbon electrode from bottom to top
Chemical method prepares the technique of carbon quantum dot, and particularly a kind of mixture with ionic liquid and nitrile prepares solid carbon as electrolyte
The method of quantum dot, and the carbon quantum dot of preparation is applied to metal ion detection field.
Background technology：
Carbon quantum dot is a kind of Novel Carbon Nanomaterials, with abundant raw material, stable in properties, small toxicity, biocompatibility
Many advantages are waited well, and there is huge application potential in fields such as cell imaging, photoelectricity, biochemical sensors.At present, had
Many reports prepared on carbon quantum dot method, are broadly divided into two major class from top to bottom and from bottom to top, and wherein the former is main
By lift-off technology from large-sized carbon source materials (such as：Graphite, CNT, carbon fiber etc.) peel off lower carbon nano-particle, bag
Laser lift-off, arc discharge method, electrochemical oxidation process etc. are included, this class method is simple to operate, abundant raw material, can in high volume give birth to
Carbon quantum dot is produced, but generally requires more complicated carbon quantum dot separation and purification treatment step；The latter it is general with organic molecule (such as：
Glucose) it is raw material, these molecules are converted into carbon quantum dot by way of carbonization, including hydro-thermal method, microwave method etc., this
Carbon quantum dot pattern and size is easily controlled, surface is easily modified that class method synthesizes, but it is suitable specific to generally require selection
Raw molecule.And, the form of the carbon quantum dot that all above methods are prepared generally dispersion soln, with solid-state form phase
Than the storage and transport of the carbon quantum dot of solution form are all inconvenient, in order to obtain solid-state carbon quantum dot, generally require freezing dry
Dry mode carries out processing carbon quantum dot solution, and time-consuming for this processing mode, and needs special instrument and equipment.Therefore, explore
A kind of method right and wrong for having from top to bottom and from bottom to top two methods advantage concurrently, simply and efficiently preparing solid carbon quantum dot
Often it is necessary.
The electrochemical method for disclosing report in the prior art has device and manufacturing process relative to other methods
The advantage such as simple, but currently used for producing the electrochemical method of carbon quantum dot to be generally top-down mode, using carbon containing electricity
Pole such as graphite rod or 3D Graphenes are used as anode, while provide the raw material for preparing carbon quantum dot, anode quilt in process of production
Constantly peel off so as to carbon quantum dot is obtained, this causes damage to electrode.At present, can be used for electrochemical method generation quantum dot
There are reports for electrolytic buffer, such as the mixed liquor containing ionic liquid, ethanol doping NaOH solution and PBS buffers,
Wherein produce efficiency during carbon quantum dot higher based on the electrolyte containing ionic liquid, while ion liquid functionalization can be obtained
Carbon quantum dot；Also studies have reported that using 3D Graphenes as anode, using the mixed liquor of acetonitrile and ionic liquid as electricity
Solution matter prepares carbon quantum dot, but 3D Graphenes synthesis high cost, so limiting the large-scale production and application of carbon quantum dot.Cause
This, seeks a kind of preparation method of solid-state carbon quantum dot, using carbon source raw material cheap and easy to get, the electrochemistry side of lossless electrode
Method prepares carbon quantum dot and has very important significance and application value.
The content of the invention：
It is an object of the invention to the shortcoming for overcoming prior art to exist, design provide a kind of non-carbon electrode, abundant raw material,
Low cost, the preparation method of solid-state carbon quantum dot rapidly and efficiently, from bottom to top.
To achieve these goals, the technique of present invention preparation carbon quantum dot specifically includes following steps：
(1) by ionic liquid and nitriles substance by volume >=1:1000 ratio is well mixed as electrolyte and is put into
In electrolytic cell of the volume more than 5mL；
(2) it is not less than 1.0cm from two areas2Platinum plate electrode be put into electrolytic cell respectively as anode and negative electrode,
Anode and negative electrode are connected with the positive pole and negative pole of power supply respectively, are switched on power, and the direct current constant voltage reaction 3-36 for applying 5-20V is small
When, electrolyte is first changed into dark-brown from colourless in course of reaction, finally has dark brown solid material to generate and adhere in negative electrode, electricity
Solution liquid is changed into stopping applied voltage after light brown again, dark brown solid material is automatic dropped to from negative electrode solution obtain doped with
The light brown solution of solid matter；
(3) the obtained light brown solution doped with solid matter of step (2) is carried out into suction filtration using prior art, and will
The solid matter that suction filtration is obtained is placed in vacuum drying chamber after being dried under the conditions of 50-100 DEG C and is transferred to clean container
Solid carbon quantum dot is obtained in ware.
Ionic liquid of the present invention selects commercial goods, nitriles substance all nitriles such as including acetonitrile and 3- methylamino propionitrile
One kind of class material.
Solid-state carbon quantum dot prepared by the present invention can obtain settled solution after adding water dissolves, illustrate carbon quantum dot in water
With preferable dispersiveness, the settled solution for obtaining is in brilliant blue under 365nm ultra violet lamps.
Solid-state carbon quantum dot powder prepared by the present invention can be characterized using means of different, and the means for being used include
One or more in fluorescence, ultraviolet, infrared, x-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM).
Solid carbon quantum point grain diameter prepared by the present invention is uniform and less than 10nm, and average-size is 3.0 ± 0.56nm, its table
Face is rich in the groups such as carboxyl, with good water solubility；The quantum yield of carbon quantum dot is 6.3%-25.2%；By consolidating for preparing
The carbon quantum dot solution that state carbon quantum dot solution water is obtained is placed more than 3 months, and fluorescence intensity is basically unchanged, and illustrates prepared carbon
The photoluminescent property stabilization of quantum dot；And carbon quantum dot solution in be separately added into 400 μM of Ag+,Al3+,Cd2+,Co2+,Fe2+,
Hg2+,Mg2+,Mn2+,Ni2+,Pb2+,Zn2+Metal ion solution, carbon quantum dot solution fluorescence intensity is basically unchanged, but adds iron
Ion (Fe3+) then there is substantially reduction, and with addition Fe3+Concentration increases and constantly reduces, and reduces fluorescence intensity and Fe3+Concentration
It is linear within the specific limits, so the solid-state carbon quantum dot for preparing can be by its fluorescent quenching effect to Fe3+To spy
Opposite sex detection.
The present invention compared with prior art, with advantages below：One is lossless electrode, and electrode is Pt plate electrodes；Two are
The method has two kinds of advantages of carbon quantum dot synthetic method from top to bottom and from bottom to top, the carbon quantum dot pattern for being generated concurrently
It is easily controlled with size, surface is easily modified, the carbon source and carbon source raw material that nitriles substance provides carbon quantum dot are readily available；Three are
Synthesis low cost, electrolyte is the mixed liquor of a small amount of ionic liquid and a large amount of nitriles substances, the complete acetonitrile of unreacted it is retortable it
After reuse；Four is the carbon quantum dot that solid-state form is can obtain without the cumbersome processing mode such as freeze-drying, processing mode
Simply, it is easy to operate；Its preparation process is simple, and easy to operate, principle is easy to get, low cost, and the solid-state carbon quantum dot of preparation is water-soluble
It is good, photoluminescent property stabilization, it is easy to storage and transport.
Brief description of the drawings：
Fig. 1 is the apparatus structure principle schematic that the present invention prepares carbon quantum dot, including power supply 1, positive pole 2, negative pole
3rd, electrolytic cell 4, electrolyte 5, anode 6 and negative electrode 7.
Fig. 2 is the transmission electron microscope picture and high-resolution-ration transmission electric-lens figure (illustration) of carbon quantum dot of the invention.
Fig. 3 is the particle size distribution figure of carbon quantum dot of the invention.
Fig. 4 is carbon quantum dot of the present invention using preparation in embodiment 1, and 400 μM are added in the carbon quantum dot of same concentration
Different metal ions, the ratio of fluorescence intensity after being quenched and the fluorescence intensity of original carbon quantum dot.
Fig. 5 is the Fe of addition various concentrations in the carbon quantum dot that the present invention is prepared in the embodiment 1 of same concentration3+Afterwards glimmering
Luminous intensity.
Fig. 6 detects Fe for the present invention using carbon quantum dot is prepared in embodiment 13+Linear relationship, with the carbon quantum dot of concentration
The Fe of middle addition various concentrations3+Afterwards, fluorescence intensity (Y) and Fe3+Linear relationship between concentration (x), curve a is Y=
844.03-1.42X and curve b is Y=509.62-0.29X.
Specific embodiment：
Below by embodiment and with reference to accompanying drawing, the present invention is further described.
Embodiment 1：
The present embodiment prepare solid-state carbon quantum dot detailed process be：
(1) it is 1.0cm to use area2Platinum plate electrode is used as the anode 6 and negative electrode 7 in electrochemical method；
(2) according to volume ratio it is 1 by ionic liquid and acetonitrile:It is put into as electrolyte 5 after 500 ratio mixing
In 100mL electrolytic cells 4,1 is turned on the power, the direct current constant voltage for implementing 15.0V in anode 6 and the two ends of negative electrode 7 reacts 24h, obtains
Dark-brown solution, after reaction terminates, electric current stablizes constant, and electrolyte 5 is changed into dark-brown from water white transparency, finally in negative electrode 7
There is dark brown solid material to generate and adhere to, electrolyte 5 stops applied voltage after being changed into light brown again, and dark brown solid material is certainly
It is dynamic that the light brown solution that solution obtains doped with solid matter is dropped to from electrode；
(3) the obtained light brown solution doped with solid matter of step (2) is carried out into suction filtration using prior art, will be taken out
The solid matter that obtains of filter is placed on after being dried in vacuum drying chamber to be transferred in clean container ware and obtains solid carbon amount
Son point powder, the water for taking the addition 10mL of 5mg is dissolved, and can obtain the carbon quantum dot solution of light yellow clarification, illustrates carbon amounts
Son point has preferably water solubility, and the solution is in brilliant blue under 365nm ultra violet lamps.
Embodiment 2：
The carbon quantum dot solution that the present embodiment prepares embodiment 1 is applied to Fe3+The context of detection of specific ion, to carbon
400 μM of Ag are separately added into quantum dot solution+,Al3+,Cd2+,Co2+,Fe2+,Hg2+,Mg2+,Mn2+,Ni2+,Pb2+,Zn2, and
Its fluorescence intensity is surveyed under the excitation wavelength of 355nm, the fluorescence intensity of gained is almost identical with stoste, as shown in Figure 4；Add
400 μM of Fe3+Substantially find that fluorescence intensity declines to a great extent, illustrate obtained carbon quantum dot to Fe3+Detection have extremely strong spy
The opposite sex and selectivity；Fe is added in order to probe into3+Concentration (10-1200 μM) and fluorescence intensity linear relationship, by a series of concentration
The Fe of gradient3+Solution is added in the carbon quantum dot solution of 3.0mL, Fe3+Solution concentration be respectively 0,5 μM, 10 μM, 20 μM, 40
μM、60μM、80μM、100μM、120μM、140μM、160μM、180μM、200μM、240μM、280μM、360μM、400μM、500μ
M, 600 μM, 700 μM, 800 μM, 900 μM, 1000 μM, 1000 μM and 1200 μM, obtain a series of different fluorescence intensities, so that
Obtain Fe3+Influence to the fluorescence intensity of carbon quantum dot, as shown in figure 5, can be realized using carbon quantum dot prepared by embodiment 1
Lowest detection is limited to 10 μM of Fe3+Detection, Fig. 6 is to add different Fe3+, fluorescence intensity (Y) and Fe3+The linear pass of concentration (X)
System, a is Y=844.03-1.42X, and b is Y=509.62-0.29X.
Claims (4)
1. a kind of preparation method of solid-state carbon quantum dot, it is characterised in that specifically include following steps：
(1) by ionic liquid and nitriles substance by volume >=1:1000 ratio is well mixed as electrolyte and is put into volume
In electrolytic cell more than 5mL；Wherein nitriles substance includes the one kind in acetonitrile and 3- methylamino propionitrile；
(2) it is not less than 1.0cm from two areas2Platinum plate electrode be put into electrolytic cell respectively as anode and negative electrode, anode and
Negative electrode is connected with the positive pole and negative pole of power supply respectively, is switched on power, and applies the direct current constant voltage reaction of 5-20V 3-36 hours, instead
Electrolyte is first changed into dark-brown from colourless during answering, and finally has dark brown solid material to generate and adhere in negative electrode, electrolyte
Stop applied voltage after being changed into light brown again, dark brown solid material drops to solution and obtains doped with solid-state from negative electrode automatically
The light brown solution of material；
(3) the obtained light brown solution doped with solid matter of step (2) is carried out into suction filtration using prior art, and by suction filtration
The solid matter for obtaining is placed in vacuum drying chamber after being dried under the conditions of 50-100 DEG C and is transferred in clean container ware
Obtain solid carbon quantum dot.
2. the preparation method of solid-state carbon quantum dot according to claim 1, it is characterised in that the ionic liquid is from commercially available
Commodity.
3. the preparation method of solid-state carbon quantum dot according to claim 1, it is characterised in that the solid-state carbon quantum dot grain of preparation
Footpath is uniform and less than 10nm, and average-size is 3.0 ± 0.56nm, and its surface is rich in carboxyl, and the quantum yield of carbon quantum dot is
6.3%-25.2%.
4. the preparation method of solid-state carbon quantum dot according to claim 1, it is characterised in that the solid-state carbon quantum dot energy of preparation
Enough by its fluorescent quenching effect to Fe3+Specific detection Fe3+。
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| KR101979288B1 (en) | 2017-08-08 | 2019-05-16 | 대구대학교 산학협력단 | Manufacturing method of carbon quantum dots by electrochemical method and manufacturing method of carbon quantum dots-silver nano particle using the same |
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| CN108085711B (en) * | 2017-12-21 | 2019-07-16 | 西安科技大学 | A kind of preparation method of the carbon quantum dot to glow |
| CN113314675B (en) * | 2020-02-27 | 2023-01-20 | 京东方科技集团股份有限公司 | Quantum dot light-emitting device, preparation method and display device |
| CN112938950B (en) * | 2021-03-19 | 2022-12-02 | 西安理工大学 | Graphene quantum dot solution prepared by electrochemical method and method |
| CN113466015B (en) * | 2021-07-20 | 2024-03-22 | 湖南智享未来生物科技有限公司 | Staining reagent for distinguishing normal cells from cancer cells, and preparation method and application thereof |
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| KR101979288B1 (en) | 2017-08-08 | 2019-05-16 | 대구대학교 산학협력단 | Manufacturing method of carbon quantum dots by electrochemical method and manufacturing method of carbon quantum dots-silver nano particle using the same |
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