CN109704312A - A kind of preparation method of water solubility blue-green fluorescent graphene quantum dot - Google Patents
A kind of preparation method of water solubility blue-green fluorescent graphene quantum dot Download PDFInfo
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- CN109704312A CN109704312A CN201910166243.5A CN201910166243A CN109704312A CN 109704312 A CN109704312 A CN 109704312A CN 201910166243 A CN201910166243 A CN 201910166243A CN 109704312 A CN109704312 A CN 109704312A
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Abstract
The invention discloses a kind of preparation methods of water-soluble blue-green fluorescent graphene quantum dot.Using top-down methods, using pyrene as presoma, by using hypotoxicity thiocarbamide as dressing agent, there is the blue-green fluorescent graphene quantum dot of good aqueous solubility in alkaline environment next step hydrothermal synthesis, synthesis process is simple and environmentally-friendly, reduces the risk of synthesis process.And the fluorescence spectrum peak wavelength of its transmitting is in 480nm or so beneficial to long wave blue wave band (460-500nm), it is expected that it is well used in the anti-blue illumination of LED light with display field.
Description
Technical field
The invention belongs to nano fluorescent material technical fields, and in particular to a kind of water solubility blue-green fluorescent graphene quantum
The preparation method of point.
Background technique
In recent years, since the peculiar property that graphene has makes it receive more and more attention, for example, it is excellent
Mechanical flexibility, big specific surface area, good chemical stability and the features such as environmentally friendly.As graphene family
Newest a member, graphene quantum dot is size in 100nm quasi-zero dimension nano material below, with two-dimensional graphene nanometer sheet and one
Dimension graphene nano line compare, zero dimension graphene quantum dot (GQDs) show stronger quantum confined effect, dimensional effect,
Boundary effect and skin effect etc.；Have many advantages, such as excellent optical characteristics, hypotoxicity and good bio-compatibility, in the sun
The fields such as energy photoelectric device, biological medicine, bio-sensing, light emitting diode (LED) have a good application prospect.
The preparation method of graphene quantum dot mainly has two major classes: method and from bottom to top method from top to bottom.Method from top to bottom
Be by the way that large-sized graphene is either physically or chemically cut small sized GQDs, including hydro-thermal method, electrochemical process and
Chemical stripping carbon fiber method；Method, which refers to, from bottom to top does precursor with small molecule, prepares GQDs by molecule route, mainly there is hydro-thermal
Method, solution chemical method, ultrasonic method and microwave method.The blue light graphene quantum dot largely prepared at present belongs to oil-soluble amount
Sub-, solubility is very poor in water.Therefore, a kind of graphene amount of new blue-green fluorescent with good aqueous solubility is developed
The method of son point is of great significance.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of water-soluble blue-green fluorescent graphene quantum dot.The present invention
Using top-down methods, using pyrene as presoma, by using hypotoxicity thiocarbamide as dressing agent, in alkaline environment next step water
Thermal synthesis has the blue-green fluorescent graphene quantum dot of good aqueous solubility, and synthesis process is simple and environmentally-friendly, reduces synthesis process
Risk.And the fluorescence spectrum peak wavelength of its transmitting is in 480nm or so beneficial to long wave blue wave band (460-
500nm), it is expected that it is well used in the anti-blue illumination of LED light with display field.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of water solubility blue-green fluorescent graphene quantum dot, includes the following steps:
1) 12.5g pyrene is weighed in the glass reaction kettle of 5L, and 1L concentrated nitric acid is added and carries out nitration reaction, reaction temperature is 80 DEG C,
Solution is sufficiently stirred, reaction is cooled to room temperature afterwards for 24 hours；
2) 2L ultrapure water is added to be diluted, is filtered with 0.22 μm of cellulose mixture filter membrane, filter and use ultrapure water
It removes remaining acid, after suction filtration, the solid on filter paper is put in culture dish, dry 2h, obtains Huang in 80 DEG C of baking ovens
Color intermediate product 1.3.6- trinitro- pyrene；
3) appropriate alkaline matter is taken to be dissolved in the alkaline solution for forming that concentration is 0.01-1.0mol/L in pure water, then by 1.3.6- tri-
Nitropyrene and dressing agent are that 1:1-1:5 is successively scattered in solution and forms 1.3.6- trinitro- pyrene concentration and be according to mass ratio
Then the mixed solution of 0.01-0.05mol/L carries out Ultrasonic Pulverization two hours；
4) it takes ultrasonic rear suspension liquid 100ml to be transferred in 150mL polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature
Degree is 180 ~ 240 DEG C, and the reaction time is that 5 ~ 10h is filtered after reaction kettle is cooled to room temperature with 0.22 μm of filter membrane；
5) filtrate is transferred in the bag filter of 1000-3500D and is dialysed 2-4 days, a water is changed within every 24 hours, at 80 DEG C after dialysis
Dry collect obtains graphene quantum dot powder in baking oven.
Alkaline matter in step 3) is NaOH, NaHCO3, ammonium hydroxide, one of KOH or several.
In step 3), dressing agent used is thiocarbamide.
Compared with the prior art, the advantages of the present invention are as follows:
The present invention uses top-down methods, using pyrene as presoma, by using hypotoxicity thiocarbamide as dressing agent, in alkaline ring
Border next step hydrothermal synthesis has gone out the blue-green fluorescent graphene quantum dot with good aqueous solubility, and synthesis process is simple and environmentally-friendly,
The risk for reducing synthesis process prepares graphene quantum dot scheme phase using hydrazine hydrate and trinitro- pyrene with what is reported at present
Than water can be quickly dissolved in after graphene quantum dot powder prepared by the present invention is dry, and the red shift of peak wavelength is left to 480nm
The right side, in beneficial long wave blue wave band (460-500nm), it is expected that it is obtained preferably in the anti-blue illumination of LED and display field
Using.
The present invention uses thiocarbamide and NaOH to be grafted onto quantum dot surface in the synthesis process as dressing agent simultaneously, forms table
Face hydrophilic radical improves the water solubility of synthesis quantum dot, is difficult after drying with the blue-green quantum dot of existing method preparation
Soluble in water to compare, the solubility of present invention water solubility blue-green fluorescent quantum dot can reach 1.5-2.0mg/mL, modify simultaneously
Agent can provide electron-withdrawing group, and the wavelength of fluorescence of GQDS is made to generate red shift (referring to Fig. 4).
Detailed description of the invention
Fig. 1 is quantum dot TEM spectrogram prepared by the present invention；
Fig. 2 is that quantum dot prepared by the present invention absorbs spectrogram, excitation spectrogram and fluorescent emission spectrogram；
Fig. 3 is the fluorescence spectra that the quantum dot solution of 1-3 of embodiment of the present invention preparation is tested under the same conditions；
Fig. 4 is the fluorescence spectra that quantum dot prepared by embodiment 2 and comparative example 1 is tested under the same conditions.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1:
12.5g pyrene is weighed in the three-neck flask of 5L, 1L concentrated nitric acid is added and carries out nitration reaction, reaction temperature is 80 DEG C, sufficiently
Agitating solution, reaction is for 24 hours；2L ultrapure water is added after being cooled to room temperature to be diluted, filtered, rinsed, remove remaining acid.
After suction filtration, product is put in culture dish, dry 2h, obtains yellow intermediate product 1.3.6- trinitro- in 80 DEG C of baking ovens
Pyrene.100ml pure water successively is dispersed by 0.4gNaOH, 1.1g thiocarbamide and 0.5g 1.3.6- trinitro- pyrene, uses ultrasonic grinder
Ultrasound 2 hours, obtains well-mixed suspension；Then reaction solution is transferred in the ptfe autoclave of 150mL, it is close
It is honored as a queen to be put into baking oven and carries out hydro-thermal reaction, reaction temperature is 200 DEG C, and the reaction time is 10 hours；It is taken out after being cooled to room temperature
Solution is filtered, and filtrate is collected.Sampling part filtrate carries out fluorescence intensity contrast test, is then transferred to residual filtrate
It dialyses 2 days in the bag filter of 1000-3500D, changes a water within every 24 hours, dry collect obtains stone in 80 DEG C of baking ovens after dialysis
Black alkene quantum dot powder.
Embodiment 2:
The 1.3.6- trinitro- pyrene prepared using embodiment 1, successively by tri- nitre of 0.4gNaOH, 2.2g thiocarbamide and 0.5g 1.3.6-
Base pyrene is scattered in 100ml pure water, with ultrasonic grinder ultrasound 2 hours, is then transferred to above-mentioned broken suspension
It is put into the ptfe autoclave of 150mL, after sealing in baking oven and carries out hydro-thermal reaction, reaction temperature is 200 DEG C, when reaction
Between be 10 hours；Solution is taken out after being cooled to room temperature, is filtered, filtrate is collected.Sampling part filtrate carries out fluorescence intensity pair
Than test, then residual filtrate is transferred in the bag filter of 1000-3500D and is dialysed 2 days, change within every 24 hours a water, dialysed
Dry collect obtains graphene quantum dot powder in 80 DEG C of baking ovens afterwards.
Embodiment 3:
The 1.3.6- trinitro- pyrene prepared using embodiment 1, successively by 0gNaOH, 2.2g thiocarbamide and 0.5g 1.3.6- trinitro-
Pyrene is scattered in 100ml pure water, with ultrasonic grinder ultrasound 2 hours, obtains suspension；Then above-mentioned suspension is transferred to
It is put into the ptfe autoclave of 150mL, after sealing in baking oven and carries out hydro-thermal reaction, reaction temperature is 200 DEG C, when reaction
Between be 10 hours；Solution is taken out after being cooled to room temperature, is filtered, filtrate is collected.Sampling part filtrate carries out fluorescence intensity pair
Than test, then residual filtrate is transferred in the bag filter of 1000-3500D and is dialysed 2 days, change within every 24 hours a water, dialysed
Dry collect obtains graphene quantum dot powder in 80 DEG C of baking ovens afterwards.
Comparative example 1:
Using pure water as solvent, take it is dried in 0.5g embodiment 1 after 1.3.6- trinitro- pyrene be dispersed in 100mL ultrapure water,
2mL hydrazine hydrate is added, with ultrasonic grinder ultrasound 2 hours；Suspension after ultrasound is transferred to the polytetrafluoroethyl-ne of 150mL
It in alkene reaction kettle, reaction kettle is sealed to be put into baking oven carries out hydro-thermal reaction, reaction temperature is 200 DEG C, the reaction time 10
Hour；Solution is taken out after being cooled to room temperature, is filtered with 0.22 μm of filter membrane, filtrate is collected；Sampling part filtrate carries out fluorescence intensity
Then residual filtrate is transferred in the bag filter of 1000-3500D and dialyses 2 days by contrast test, change a water within every 24 hours, thoroughly
Dry collect obtains graphene quantum dot powder in 80 DEG C of baking ovens after analysis.
Fig. 1 is quantum dot TEM spectrogram prepared by the embodiment of the present invention 1, as can be seen from the figure quantum prepared by the present invention
Point has apparent lattice fringe, and crystalline quality is good.
Fig. 2 is that quantum dot prepared by the embodiment of the present invention 1 absorbs spectrogram, excitation spectrogram and fluorescent emission spectrogram.From absorption
Spectrogram and exciting light spectrogram can be seen that quantum dot prepared by the present invention to be had in 270-300nm and 350-440nm wave band
It is apparent to absorb, from spectral radiation curves it can be seen that quantum dot emission goes out peak value about under the irradiation of 370nm wavelength exciting light
The blue-green fluorescent of 480nm.
Fig. 3 is the fluorescence spectra that the quantum dot solution of 1-3 of embodiment of the present invention preparation is tested under the same conditions, from figure
In it can be seen that with thiocarbamide dosage increase, fluorescence intensity enhancing；After NaOH is added, solution PH increases, the quantum dot fluorescence of preparation
Intensity becomes strong, and peak emission wavelength produces about 5-10nm red shift.
Fig. 4 is the fluorescence spectra that quantum dot prepared by embodiment 2 and comparative example 1 is tested under the same conditions, Cong Tuzhong
It can be seen that compared with the graphene quantum dot for using hydrazine hydrate to prepare, quantum fluorescent emission peak value wavelength prepared by the present invention
Red shift about 20nm or so, in beneficial to long wave blue wave band.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of preparation method of water solubility blue-green fluorescent graphene quantum dot, characterized by the following steps:
1) 12.5g pyrene is weighed in the glass reaction kettle of 5L, and 1L concentrated nitric acid is added and carries out nitration reaction, reaction temperature is 80 DEG C,
Solution is sufficiently stirred, reaction is cooled to room temperature afterwards for 24 hours；
2) 2L ultrapure water is added to be diluted, is filtered with 0.22 μm of cellulose mixture filter membrane, filter and use ultrapure water
It removes remaining acid, after suction filtration, the solid on filter paper is put in culture dish, dry 2h, obtains Huang in 80 DEG C of baking ovens
Color intermediate product 1.3.6- trinitro- pyrene；
3) appropriate alkaline matter is taken to be dissolved in the alkaline solution for forming that concentration is 0.01-1.0mol/L in pure water, then by 1.3.6- tri-
Nitropyrene and dressing agent are that 1:1-1:5 is successively scattered in solution and forms 1.3.6- trinitro- pyrene concentration and be according to mass ratio
Then the mixed solution of 0.01-0.05mol/L carries out Ultrasonic Pulverization two hours；
4) it takes ultrasonic rear suspension liquid 100ml to be transferred in 150mL polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature
Degree is 180 ~ 240 DEG C, and the reaction time is that 5 ~ 10h is filtered after reaction kettle is cooled to room temperature with 0.22 μm of filter membrane；
5) filtrate is transferred in the bag filter of 1000-3500D and is dialysed 2-4 days, a water is changed within every 24 hours, at 80 DEG C after dialysis
Dry collect obtains graphene quantum dot powder in baking oven.
2. a kind of preparation method of water-soluble blue-green fluorescent graphene quantum dot according to claim 1, feature exist
In: the alkaline matter in step 3) is NaOH, NaHCO3, ammonium hydroxide, one of KOH or several.
3. a kind of preparation method of water-soluble blue-green fluorescent graphene quantum dot according to claim 1, feature exist
In: in step 3), dressing agent used is thiocarbamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111977640A (en) * | 2020-08-28 | 2020-11-24 | 泉州师范学院 | Preparation method of green fluorescent graphene quantum dot powder |
| CN114836772A (en) * | 2022-05-25 | 2022-08-02 | 河北工业大学 | Preparation method and application of metal oxide loaded graphene quantum dot composite catalyst |
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| CN104812697A (en) * | 2012-11-29 | 2015-07-29 | 北京奈艾斯新材料科技有限公司 | Method for forming nitrogen and sulfur co-doped graphene quantum dots |
| CN105670619A (en) * | 2016-02-25 | 2016-06-15 | 浙江理工大学 | Sulfur-doping graphene quantum dot, preparation method of sulfur-doping graphene quantum dot and application of lead ion detection |
| CN106883849A (en) * | 2017-03-29 | 2017-06-23 | 温州医科大学 | Graphene quantum dot that a kind of nitrogenous sulphur mixes and preparation method thereof and the application on lysine luciferase assay reagent is prepared |
| CN108529604A (en) * | 2018-07-10 | 2018-09-14 | 泉州师范学院 | A kind of preparation method of graphene quantum dot |
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Patent Citations (4)
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| CN104812697A (en) * | 2012-11-29 | 2015-07-29 | 北京奈艾斯新材料科技有限公司 | Method for forming nitrogen and sulfur co-doped graphene quantum dots |
| CN105670619A (en) * | 2016-02-25 | 2016-06-15 | 浙江理工大学 | Sulfur-doping graphene quantum dot, preparation method of sulfur-doping graphene quantum dot and application of lead ion detection |
| CN106883849A (en) * | 2017-03-29 | 2017-06-23 | 温州医科大学 | Graphene quantum dot that a kind of nitrogenous sulphur mixes and preparation method thereof and the application on lysine luciferase assay reagent is prepared |
| CN108529604A (en) * | 2018-07-10 | 2018-09-14 | 泉州师范学院 | A kind of preparation method of graphene quantum dot |
Cited By (2)
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| CN111977640A (en) * | 2020-08-28 | 2020-11-24 | 泉州师范学院 | Preparation method of green fluorescent graphene quantum dot powder |
| CN114836772A (en) * | 2022-05-25 | 2022-08-02 | 河北工业大学 | Preparation method and application of metal oxide loaded graphene quantum dot composite catalyst |
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