CN105316697A - Preparation method for solid-state carbon quantum dot - Google Patents
Preparation method for solid-state carbon quantum dot Download PDFInfo
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- CN105316697A CN105316697A CN201510903400.8A CN201510903400A CN105316697A CN 105316697 A CN105316697 A CN 105316697A CN 201510903400 A CN201510903400 A CN 201510903400A CN 105316697 A CN105316697 A CN 105316697A
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Abstract
The invention belongs to the technical field of preparation of carbon quantum dot materials, and relates to a preparation method for solid-state carbon quantum dots. The preparation method comprises the following steps: firstly, mixing an ionic liquid with nitrile substances, and putting the mixture, as an electrolytic solution, into an electrolytic tank; respectively selecting two platinum electrodes, of which the area is no smaller than 1.0 cm<2>, as an anode and a cathode, and putting the anode and the cathode into the electrolytic tank, and switching on a power supply to react, thereby obtaining a light brown solution mixed with solid-state substances; then, carrying out suction filtration on the light brown solution mixed with the solid-state substances, carrying out vacuum-drying on the solid substances obtained by suction filtration, and transferring the solid substances into a clean container vessel, thereby obtaining the solid-state carbon quantum dots. The preparation method is simple in preparation process, convenient in operation, accessible in principle, and low in cost; the prepared solid-state carbon quantum dots are good in water solubility, stable in fluorescent property, and easy to store and transport.
Description
Technical field:
The invention belongs to carbon quantum dot material preparing technical field, relate to a kind of technique of the electrochemical production carbon quantum dot based on non-carbon dioxide process carbon electrode from bottom to top, particularly with the mixture of ionic liquid and nitrile for the method for solid carbon quantum dot prepared by electrolytic solution, 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, has the many advantages such as abundant raw material, stable in properties, toxicity are little, good biocompatibility, has huge application potential in fields such as cell imaging, photoelectricity, biochemical sensors.At present, there is the report much prepared about carbon quantum dot method, mainly be divided into two large classes and from bottom to top from top to bottom, wherein the former peels off lower carbon nano-particle mainly through lift-off technology from large-sized carbon source materials (as: graphite, carbon nanotube, carbon fiber etc.), comprise laser lift-off, arc discharge method, electrochemical oxidation process etc., these class methods are simple to operate, abundant raw material, can be mass-produced carbon quantum dot, but the carbon quantum dot separation and purification treatment step that general needs are more complicated; The latter generally with organic molecule (as: glucose) for starting material, by the mode of carbonization by these Molecular Cloning be carbon quantum dot, comprise hydrothermal method, microwave method etc., these class methods synthesis carbon quantum dot pattern and size easily controls, surface is easily modified, but generally need to choose suitable specified raw material molecule.And, the carbon quantum dot that all aforesaid methods are prepared is generally the form of dispersion soln, compared with solid-state form, the storage of the carbon quantum dot of solution form and transport are all inconvenient, in order to obtain solid carbon quantum dot, generally need lyophilize mode to carry out process carbon quantum dot solution, this processing mode length consuming time, and need special plant and instrument.Therefore, a kind of to have concurrently from top to bottom and two kinds of method advantages, the method for preparing solid carbon quantum dot simply, are efficiently necessary is explored from bottom to top.
In prior art, the electrochemical method of open report has device relative to other method and the advantage such as making processes is simple, but the electrochemical method at present for generation of carbon quantum dot is generally top-down mode, adopt carbon-containing electrode if graphite rod or 3D Graphene are as anode, the starting material of preparation carbon quantum dot are provided simultaneously, anode is constantly peeled off thus obtained carbon quantum dot in process of production, and this causes damage to electrode.At present, there are reports to can be used for the electrolytic buffer of electrochemical method manufacturing quantum dot, as the mixed solution containing ionic liquid, ethanol doping NaOH solution and PBS buffer reagent etc., efficiency when wherein producing carbon quantum dot based on the ionogen containing ionic liquid is higher, can obtain the carbon quantum dot of ion liquid functionalization simultaneously; Also studies have reported that and adopt 3D Graphene as anode, adopt the mixed solution of acetonitrile and ionic liquid to prepare carbon quantum dot as ionogen, but 3D Graphene synthesis cost is high, so limit scale operation and the application of carbon quantum dot.Therefore, seek a kind of preparation method of solid carbon quantum dot, utilize carbon source starting material cheap and easy to get, the electrochemical method of harmless electrode is prepared carbon quantum dot and is had very important significance and using value.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, design provides that a kind of non-carbon dioxide process carbon electrode, abundant raw material, cost are low, the preparation method of solid carbon quantum dot rapidly and efficiently, from bottom to top.
To achieve these goals, the technique that the present invention prepares carbon quantum dot specifically comprises the following steps:
(1) using ionic liquid and nitriles substance by volume >=ratio of 1:1000 mixes as electrolytic solution and puts into the electrolyzer that volume is greater than 5mL;
(2) two areas are selected to be not less than 1.0cm
2platinum plate electrode put into electrolyzer respectively as anode and negative electrode, anode and negative electrode are communicated with negative pole with the positive pole of power supply respectively, switch on power, apply the direct current constant voltage reaction 3-36 hour of 5-20V, in reaction process, electrolytic solution first becomes dark-brown from colourless, finally have dark brown solid material generate and adhere at negative electrode, electrolytic solution becomes again after light brown and stops applying voltage, and dark brown solid material drops to from negative electrode the light brown solution that solution obtains doped with solid matter automatically;
(3) adopt prior art to carry out suction filtration the light brown solution doped with solid matter obtained for step (2), and the solid matter that suction filtration is obtained be placed under 50-100 DEG C of condition, carry out drying in vacuum drying oven after be transferred in clean container ware and namely obtain solid carbon quantum dot.
Ionic liquid of the present invention selects commercial goods, and nitriles substance comprises the one of all nitriles substances such as acetonitrile and 3-methylamino-propionitrile.
Can obtain settled solution after solid carbon quantum dot prepared by the present invention adds water dissolution, illustrate that carbon quantum dot has good dispersiveness in water, the settled solution obtained is brilliant blue under 365nm ultra violet lamp.
Solid carbon quantum dot powder prepared by the present invention can adopt means of different to characterize, the means adopted comprise in fluorescence, ultraviolet, infrared, x-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM) one or more.
Evenly and be less than 10nm, mean sizes is 3.0 ± 0.56nm to solid carbon quantum point grain diameter prepared by the present invention, and its rich surface, containing groups such as carboxyls, has well water-soluble; The quantum yield of carbon quantum dot is 6.3%-25.2%; The carbon quantum dot solution that the solid carbon quantum dot solution water of preparation obtains is placed more than 3 months, and fluorescence intensity is substantially constant, illustrates that the photoluminescent property of prepared carbon quantum dot is stablized; And carbon quantum dot solution in add 400 μMs of Ag respectively
+, Al
3+, Cd
2+, Co
2+, Fe
2+, Hg
2+, Mg
2+, Mn
2+, Ni
2+, Pb
2+, Zn
2+metal ion solution, carbon quantum dot solution fluorescence intensity is substantially constant, but adds iron ion (Fe
3+) then there is obvious reduction, and along with adding Fe
3+concentration increases and constantly reduces, and reduces fluorescence intensity and Fe
3+concentration is linear within the specific limits, so the solid carbon quantum dot of preparation can by its fluorescent quenching effect to Fe
3+to specific detection.
The present invention compared with prior art, has the following advantages: one is that electrode is lossless, and electrode is Pt plate electrode; Two is advantages that the method has two kinds of carbon quantum dot synthetic methods and from bottom to top concurrently from top to bottom, and the carbon quantum dot pattern generated and size easily control, surface is easily modified, and nitriles substance provides the carbon source of carbon quantum dot and carbon source raw material easily obtains; Three is that synthesis cost is low, and electrolytic solution is the mixed solution of a small amount of ionic liquid and a large amount of nitriles substance, the retortable recycling afterwards of acetonitrile that unreacted is complete; Four is the carbon quantum dot that can obtain solid-state form without the need to loaded down with trivial details processing modes such as lyophilizes, and processing mode is simple, easy to operate; Its preparation process is simple, and easy to operate, principle is easy to get, and cost is low, the solid carbon quantum dot good water solubility of preparation, and photoluminescent property is stablized, and is easy to store and transport.
Accompanying drawing illustrates:
Fig. 1 is the apparatus structure principle schematic that the present invention prepares carbon quantum dot, comprising power supply 1, positive pole 2, negative pole 3, electrolyzer 4, electrolytic solution 5, anode 6 and negative electrode 7.
Fig. 2 is transmission electron microscope picture and the high-resolution-ration transmission electric-lens figure (illustration) of carbon quantum dot of the present invention.
Fig. 3 is the particle size distribution figure of carbon quantum dot of the present invention.
Fig. 4 is the carbon quantum dot that the present invention uses preparation in embodiment 1, adds 400 μMs of different metal ions, the ratio of the fluorescence intensity of the fluorescence intensity after cancellation and original carbon quantum dot in the carbon quantum dot of same concentration.
Fig. 5 is the Fe adding different concns in the carbon quantum dot prepared in the embodiment 1 of same concentration of the present invention
3+after fluorescence intensity.
Fig. 6 be the present invention use in embodiment 1 prepare carbon quantum dot detect Fe
3+linear relationship, with the Fe adding different concns in the carbon quantum dot of concentration
3+after, fluorescence intensity (Y) and Fe
3+linear relationship between concentration (x), curve a is Y=844.03-1.42X and curve b is Y=509.62-0.29X.
Embodiment:
Below by embodiment, also the present invention is further described by reference to the accompanying drawings.
Embodiment 1:
The detailed process that the present embodiment prepares solid carbon quantum dot is:
(1) area is adopted to be 1.0cm
2platinum plate electrode is as the anode 6 in electrochemical method and negative electrode 7;
(2) is put into 100mL electrolyzer 4 as electrolytic solution 5 after the ratio mixing of 1:500 using ionic liquid and acetonitrile according to volume ratio, opening power 1, the direct current constant voltage reaction 24h of 15.0V is implemented at anode 6 and negative electrode 7 two ends, obtain dark-brown solution, after reaction terminates, current stabilization is constant, electrolytic solution 5 becomes dark-brown from water white transparency, finally dark brown solid material is had to generate and adhere at negative electrode 7, electrolytic solution 5 stops applying voltage after becoming again light brown, dark brown solid material drops to from electrode the light brown solution that solution obtains doped with solid matter automatically,
(3) prior art is adopted to carry out suction filtration the light brown solution doped with solid matter obtained for step (2), the solid matter obtained by suction filtration is transferred in clean container ware after being placed on and carrying out drying in vacuum drying oven and is namely obtained solid carbon quantum dot powder, the water adding 10mL getting 5mg dissolves, the carbon quantum dot solution of light yellow clarification can be obtained, illustrate that carbon quantum dot has water-soluble preferably, this solution is brilliant blue under 365nm ultra violet lamp.
Embodiment 2:
The carbon quantum dot solution that embodiment 1 is prepared by the present embodiment is applied to Fe
3+the context of detection of specific ion, adds 400 μMs of Ag respectively in carbon quantum dot solution
+, Al
3+, Cd
2+, Co
2+, Fe
2+, Hg
2+, Mg
2+, Mn
2+, Ni
2+, Pb
2+, Zn
2, and survey its fluorescence intensity under the excitation wavelength of 355nm, identical almost with stoste of the fluorescence intensity of gained, as shown in Figure 4; Add the Fe of 400 μMs
3+obvious discovery fluorescence intensity declines to a great extent, and illustrates that obtained carbon quantum dot is to Fe
3+detection there is extremely strong specificity and selectivity; Fe is added in order to probe into
3+concentration (10-1200 μM) and fluorescence intensity linear relationship, by the Fe of a series of concentration gradient
3+solution joins in the carbon quantum dot solution of 3.0mL, Fe
3+strength of solution is respectively 0,5 μM, 10 μMs, 20 μMs, 40 μMs, 60 μMs, 80 μMs, 100 μMs, 120 μMs, 140 μMs, 160 μMs, 180 μMs, 200 μMs, 240 μMs, 280 μMs, 360 μMs, 400 μMs, 500 μMs, 600 μMs, 700 μMs, 800 μMs, 900 μMs, 1000 μMs, 1000 μMs and 1200 μMs, obtain a series of different fluorescence intensity, thus obtain Fe
3+on the impact of the fluorescence intensity of carbon quantum dot, as shown in Figure 5, the carbon quantum dot adopting embodiment 1 to prepare can realize the Fe that lowest detection is limited to 10 μMs
3+detect, Fig. 6 adds different Fe
3+, fluorescence intensity (Y) and Fe
3+the linear relationship of concentration (X), a is Y=844.03-1.42X, b is Y=509.62-0.29X.
Claims (4)
1. a preparation method for solid carbon quantum dot, is characterized in that specifically comprising the following steps:
(1) using ionic liquid and nitriles substance by volume >=ratio of 1:1000 mixes as electrolytic solution and puts into the electrolyzer that volume is greater than 5mL;
(2) two areas are selected to be not less than 1.0cm
2platinum plate electrode put into electrolyzer respectively as anode and negative electrode, anode and negative electrode are communicated with negative pole with the positive pole of power supply respectively, switch on power, apply the direct current constant voltage reaction 3-36 hour of 5-20V, in reaction process, electrolytic solution first becomes dark-brown from colourless, finally have dark brown solid material generate and adhere at negative electrode, electrolytic solution becomes again after light brown and stops applying voltage, and dark brown solid material drops to from negative electrode the light brown solution that solution obtains doped with solid matter automatically;
(3) adopt prior art to carry out suction filtration the light brown solution doped with solid matter obtained for step (2), and the solid matter that suction filtration is obtained be placed under 50-100 DEG C of condition, carry out drying in vacuum drying oven after be transferred in clean container ware and namely obtain solid carbon quantum dot.
2. the preparation method of solid carbon quantum dot according to claim 1, it is characterized in that described ionic liquid selects commercial goods, nitriles substance comprises the one in acetonitrile and 3-methylamino-propionitrile.
3. the preparation method of solid carbon quantum dot according to claim 1, it is characterized in that the solid carbon quantum point grain diameter prepared evenly and be less than 10nm, mean sizes is 3.0 ± 0.56nm, and its rich surface is containing carboxyl, and the quantum yield of carbon quantum dot is 6.3%-25.2%.
4. the preparation method of solid carbon quantum dot according to claim 1, is characterized in that the solid carbon quantum dot prepared can by its fluorescent quenching effect to Fe
3+specific detection Fe
3+.
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| CN108085711A (en) * | 2017-12-21 | 2018-05-29 | 西安科技大学 | A kind of preparation method of the carbon quantum dot to glow |
| KR20190016354A (en) * | 2017-08-08 | 2019-02-18 | 대구대학교 산학협력단 | Manufacturing method of carbon quantum dots by electrochemical method and manufacturing method of carbon quantum dots-silver nano particle using the same |
| CN112938950A (en) * | 2021-03-19 | 2021-06-11 | 西安理工大学 | Graphene quantum dot solution prepared by electrochemical method and method |
| CN113466015A (en) * | 2021-07-20 | 2021-10-01 | 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 |
| US20220006033A1 (en) * | 2020-02-27 | 2022-01-06 | Boe Technology Group Co., Ltd. | Quantum dot light-emitting device, preparing method and display device |
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| KR20190016354A (en) * | 2017-08-08 | 2019-02-18 | 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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| US20220006033A1 (en) * | 2020-02-27 | 2022-01-06 | Boe Technology Group Co., Ltd. | Quantum dot light-emitting device, preparing method and display device |
| CN112938950A (en) * | 2021-03-19 | 2021-06-11 | 西安理工大学 | Graphene quantum dot solution prepared by electrochemical method and method |
| CN113466015A (en) * | 2021-07-20 | 2021-10-01 | 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 |
| 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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