CN105565302B - The method for carrying out graphene quantum dot preparation is aoxidized based on hypochlorite - Google Patents
The method for carrying out graphene quantum dot preparation is aoxidized based on hypochlorite Download PDFInfo
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Abstract
The invention discloses the method that progress graphene quantum dot preparation is aoxidized based on hypochlorite, concretely comprise the following steps：By solid oxidation graphite dispersion in deionized water, disperseed under ultrasonication, make graphite oxide is scattered to peel off into individual layer, obtain graphene oxide water solution；Then graphene oxide water solution and the aqueous solution containing hypochlorite are mixed at room temperature, obtain mixed solution；Irradiation 5min~3h finally is carried out to mixed solution using ultraviolet light, produces graphene quantum dot.The present invention is by means such as ultraviolet irradiations, directly reacted with graphene oxide using the hypochlorite aqueous solution with strong oxidation performance in aqueous phase system, prepare graphene quantum dot, process breviaty significantly preparation technology flow, than prior art, the inventive method reaction time foreshortened to dozens of minutes from lasting up to 20 days, and compared with the low physical method of efficiency, yield is closely up to 80%.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to one kind carries out graphene based on hypochlorite oxidation
Method prepared by quantum dot.
Background technology
Since the discovery of graphene in 2004, graphene draws because of properties such as its excellent electricity, calorifics, optics and mechanics
Basic science and the research boom of application field are played.For example, graphene has high carrier mobility (200,000cm2
V-1 s-1) and thermal conductivity (~5,000W m-1K-1), and room-temperature quantum Hall effect (Quantum Hall Effect),
It is expected to the desirable material for substituting silicon to turn into high performance electronics.However, graphene is a kind of semi-metallic of zero band gap,
This property limits its application in the field such as semiconductor devices and opto-electronic device, such as field-effect transistor (FETs).Open
Graphene band gap, it is transformed into semi-conducting material from semi-metallic, is a forward position Journal of Sex Research of graphene research field
Problem.At present, opening graphene band gap mainly includes both direction, first, being based on quantum effect, graphene is cut into nanometer
Band, nanometer sieve or quantum dot, nano-scale dimension is realized on one-dimensional or two-dimensional directional.Second, being doped to graphene and surface
Functionalization is to destroy its pi-electron conjugated system.Graphene quantum dot (GQDs) is the graphene nano that two-dimensional is less than 100nm
Piece, due to quantum effect, it has special photoelectronics property, is led in biological medicine, solar cell, opto-electronic device etc.
Domain is with a wide range of applications.
The preparation method for the relevant graphene quantum dot that document has been reported is broadly divided into from bottom to top and two kinds from top to bottom
Method.Self-absorption Correction Factor is primarily referred to as using organic molecule as presoma, forms carbon-carbon bond by chemical polycondensation reaction, will have
Machine small molecule aggregates into the graphene quantum dot with big conjugated structure.This method preparation process complexity is cumbersome, reaction time consumption
Long and productivity ratio is relatively low.In addition, GQDs easily reunites in building-up process, it is difficult to obtain the GQDs of large-size.From upper
It is using graphene or carbon fiber as raw material under and, is oxidized by chemical oxidation and cuts into quantum dot.However, utilize this method
The graphene quantum dot low yield being prepared, and the carbon conjugated backbone degree that wrecks is more serious.Ajayan et al. exists
《Nano Letters》Entitled " Graphene quantum dots derived have been delivered on (2012,12,844-849) magazine
From carbon fibers (preparing graphene quantum dot by raw material of carbon fiber) " article, the author of this article are fine using carbon
Dimension has Rotating fields, and advantage of its diameter in the nano-scale range, (concentrated sulfuric acid under the conditions of nitration mixture：Concentrated nitric acid=3:1, V/
V), high-temperature stirring, the method by aoxidizing intercalation destroy the layer structure of carbon fiber, graphene quantum dot are prepared.However,
The graphene quantum dot obtained by this method has one layer of thickness for arriving multilayer, not truly there is monoatomic layer
The graphene quantum dot of thickness.Xuejiao Zhou et al. exist《ACS Nano》(2012,6,6592) delivered on magazine entitled
“Photo-Fenton Reaction of Graphene Oxide:A New Strategy to Prepare Graphene
Quantum Dots for DNA cleavage (light auxiliary-fenton reactions of graphene oxide：One kind of graphene quantum dot
Novel processing step and its dissection research to DNA) " article, under ultraviolet light, author utilizes graphene oxide
Light auxiliary-fenton reaction, by controlling the reaction time, graphene quantum dot is successfully prepared, graphite is prepared using this method
The system of alkene quantum dot is less without using strong acid and hot conditions, accessory substance, is that a kind of reaction is a kind of fast and effectively stone
Black alkene quantum dot preparation method.However, the pH value of system needs more strictly to control in the range of 3~4, under the conditions of strong acidity
(pH<3), graphene oxide is easily reunited, as system pH>When 4, reaction rate reduces, and is primarily due to when solution alkaline,
It is unfavorable for hydroxyl radical free radical (OH) generation.In addition, there is yield in the method for preparing graphene quantum dot that presently, there are
It is low, the deficiencies of taking, it would therefore be highly desirable to seek a kind of simple and quick and prepare graphene quantum dot in the range of wider pH
New method.
The content of the invention
It is an object of the invention to provide a kind of method for being aoxidized based on hypochlorite and carrying out graphene quantum dot preparation, solve
Existing graphene quantum dot preparation process takes, the problem of the low yield of graphene quantum dot.
The technical solution adopted in the present invention is that the method for carrying out graphene quantum dot preparation is aoxidized based on hypochlorite,
Concretely comprise the following steps：
Step 1：By solid oxidation graphite dispersion in deionized water, disperseed under ultrasonication, make graphite oxide
It is scattered to peel off into individual layer, obtain graphene oxide water solution；
Step 2：Step 1 gained graphene oxide water solution and the aqueous solution containing hypochlorite are mixed at room temperature
Close, obtain mixed solution；Irradiation 5min~5h is carried out to mixed solution followed by ultraviolet light, produces graphene quantum dot.
It is of the invention to be further characterized in that,
In step 1, ultrasonication process is：It is 40kHz in frequency, disperses 1h under the ultrasonic wave that power is 160W.
The concentration of step 1 gained graphene oxide water solution is 0.01~4mg/mL.
In step 2, the aqueous solution containing hypochlorite is one kind in hypochlorous acid, sodium hypochlorite or calcium hypochlorite solution.
Available chlorine content is 1~30% in the aqueous solution containing hypochlorite.
Graphene oxide water solution is 10~100 with the aqueous solution volume ratio containing hypochlorite:1.
In step 2, the pH of gained mixed solution is 3~14.
In step 2, the wavelength of ultraviolet light is 190~400nm, and power is 100~1000W.
The invention has the advantages that the present invention, by means such as ultraviolet irradiations, being utilized in aqueous phase system has strong oxygen
The hypochlorite aqueous solution for changing performance directly reacts with graphene oxide, prepares graphene quantum dot, the process is significantly
Breviaty preparation technology flow, than prior art, the inventive method reaction time up to 20 days foreshortened to several ten points from lasting
Clock, compared with the low physical method of efficiency, yield is closely up to 80%.
Brief description of the drawings
Fig. 1 is the atomic force microscopy diagram of graphene oxide；
Fig. 2 is that the present invention aoxidizes the gained graphite of embodiment of the method 3 for carrying out graphene quantum dot preparation based on hypochlorite
The atomic force microscopy diagram of alkene quantum dot；
Fig. 3 is that the present invention aoxidizes the gained graphite of embodiment of the method 3 for carrying out graphene quantum dot preparation based on hypochlorite
Transmission electron microscopy figure under alkene quantum dot low range.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The present invention is a kind of to aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, concretely comprises the following steps：
Step 1：Using the graphene oxide that gained is prepared using Hummers methods as starting material, deionized water is dispersed in
In, disperseed under ultrasonication, make graphite oxide is scattered to peel off into individual layer, obtain graphene oxide water solution；Wherein, it is ultrasonic
Mechanism is：It is 40kHz in frequency, disperses 1h under the ultrasonic wave that power is 160W；Gained graphene oxide water solution it is dense
Spend for 0.01~4mg/mL.
Step 2：Step 1 gained graphene oxide water solution and the aqueous solution containing hypochlorite are mixed at room temperature
Close, it is 3~14 mixed solutions to obtain pH；It is 190~400nm followed by wavelength, the ultraviolet light that power is 100~1000W is to mixed
Close solution and carry out irradiation 5min~5h, produce graphene quantum dot.Wherein, the aqueous solution containing hypochlorite is hypochlorous acid, secondary
One kind in sodium chlorate or calcium hypochlorite solution.Available chlorine content is 1~30% in the aqueous solution containing hypochlorite.Aoxidize stone
Black aqueous solution is 10~100 with the aqueous solution volume ratio containing hypochlorite:1.
Embodiment 1
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 0.01mg/mL；
(2) step 1 gained graphene oxide water solution and available chlorine content are pressed into body for 1.0% aqueous sodium hypochlorite solution
Product mixes than 10 ︰ 1, and regulation solution system pH is 3, and with power 100W, the uviol lamp that dominant wavelength is 190nm irradiates to mixed solution
5h, produce graphene quantum dot.
Embodiment 2
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 0.05mg/mL；
(2) step 1 gained graphene oxide water solution and available chlorine content are pressed into body for 5.0% aqueous sodium hypochlorite solution
Product mixes than 20 ︰ 1, and regulation solution system pH is 5, and with power 200W, the uviol lamp that dominant wavelength is 254nm irradiates to mixed solution
3h, graphene quantum dot is prepared.
Embodiment 3
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 0.5mg/mL；
(2) step 1 gained graphene oxide water solution and available chlorine content are pressed into body for 5.0% aqueous sodium hypochlorite solution
Product mixes than 30 ︰ 1, and regulation solution system pH is 10, with the uviol lamp that power 1000W, dominant wavelength are 254nm to mixed solution spoke
According to 10min, graphene quantum dot is produced.
From atomic force microscopy diagram (Fig. 2) and transmission electron microscope figure (Fig. 3) as can be seen that gained graphene quantum dot
Its two-dimensional is reduced to 20-30 nanoscales from micron order compared with graphene oxide (Fig. 1), and Size Distribution is homogeneous, and only
One atomic layer level thickness.
Embodiment 4
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 0.5mg/mL；
(2) step 1 gained graphene oxide water solution is pressed with available chlorine content for the 15.0% calcium hypochlorite aqueous solution
The ︰ 1 of volume ratio 50 is mixed, and regulation solution system pH is 10, and with power 500W, dominant wavelength is 365nm uviol lamp to mixed solution
30min is irradiated, graphene quantum dot is prepared.
Embodiment 5
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 1.0mg/mL；
(2) step 1 gained graphene oxide water solution is pressed with available chlorine content for 20.0% aqueous sodium hypochlorite solution
The ︰ 1 of volume ratio 50 is mixed, and regulation solution system pH is 14, and with power 1000W, dominant wavelength is 365nm uviol lamp to mixed solution
15min is irradiated, graphene quantum dot is prepared.
Embodiment 6
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 4.0mg/mL；
(2) step 1 gained graphene oxide water solution and available chlorine content are pressed into volume for 30% hypochloric acid water solution
Mixed than 100 ︰ 1, regulation solution system pH is 14, and with power 1000W, dominant wavelength is 400nm uviol lamp to mixed solution spoke
According to 15min, graphene quantum dot is produced.
Embodiment 7
Using graphene oxide water solution as starting material, under ultraviolet radiation, oxidation system is carried out to it using hypochlorite
Standby graphene quantum dot, specifically includes following steps：
(1) it is graphene oxide solid is scattered in deionized water, under frequency 40kHz, power 160W ultrasonication
Scattered 1h, scattered peel off of graphite oxide into individual layer, is obtained into the graphene oxide water solution that concentration is 0.5mg/mL；
(2) step 1 gained graphene oxide water solution is pressed with available chlorine content for 10.0% aqueous sodium hypochlorite solution
The ︰ 1 of volume ratio 30 is mixed, and regulation solution system pH is 7, and with power 1000W, dominant wavelength is 365nm uviol lamp to mixed solution
5min is irradiated, produces graphene quantum dot.
The power of ultraviolet light and the dosage of hypochlorite directly influence the preparation efficiency of product in the inventive method, secondary
Chloric acid, sodium hypochlorite and calcium hypochlorite are common oxidant, are widely used in the fields such as bleaching, Industrial Wastewater Treatment, its own
Easily decompose and form oxygen radical, when being reacted with organic molecule, micromolecular compound can be oxidized to.Graphite oxide
Alkene is considered as the containing oxygen derivative of graphene, and a large amount of oxygen-containing functional groups and defect are contained in its conjugated structure surface, chemically
It is a kind of organic conjugated molecule with larger molecular weight for angle.And hypochlorite is easier the carbon atom with fault location
React, and the more complete region of conjugated backbone structure is retained, graphene oxide is finally oxidized and cut and shape
It is less than 100nm nanometer sheet, i.e. graphene quantum dot into two-dimensional.Simultaneously as the active material for participating in reaction be oxygen from
By base, so reaction can be rapidly completed within the extremely short time, and the dosage of hypochlorite directly affects graphene quantum dot
Output capacity, therefore, the addition of hypochlorite need to be controlled strictly.In addition, in certain density graphene oxide water solution and
Under the conditions of hypochlorite content, when the power of ultraviolet light increases to 1000W by 500W, the time required to prepared by graphene quantum dot
15min is shortened to by 1h.
Claims (6)
1. the method for carrying out graphene quantum dot preparation is aoxidized based on hypochlorite, it is characterised in that concretely comprise the following steps：
Step 1：By solid oxidation graphite dispersion in deionized water, disperseed under ultrasonication, disperse graphite oxide
Individual layer is peeled off into, obtains graphene oxide water solution, ultrasonication process is：It is 40kHz in frequency, power is 160W ultrasonic wave
Disperse 1h down；
Step 2：Step 1 gained graphene oxide water solution and the aqueous solution containing hypochlorite are mixed at room temperature,
Mixed solution is obtained, the concentration of gained graphene oxide water solution is 0.01~4mg/mL；Followed by ultraviolet light to mixed solution
Irradiation 5min~5h is carried out, produces graphene quantum dot.
2. according to claim 1 aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, its feature exists
In in step 2, the aqueous solution containing hypochlorite is one kind in hypochlorous acid, sodium hypochlorite or calcium hypochlorite solution.
3. according to claim 2 aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, its feature exists
In available chlorine content is 1~30% in the aqueous solution containing hypochlorite.
4. according to claim 1 aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, its feature exists
In graphene oxide water solution is 10~100 with the aqueous solution volume ratio containing hypochlorite:1.
5. according to claim 1 aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, its feature exists
In in step 2, the pH of gained mixed solution is 3~14.
6. according to claim 1 aoxidize the method for carrying out graphene quantum dot preparation based on hypochlorite, its feature exists
In in step 2, the wavelength of ultraviolet light is 190~400nm, and power is 100~1000W.
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| CN108946716A (en) * | 2018-09-30 | 2018-12-07 | 西安理工大学 | A kind of method that anacidity method prepares graphene quantum dot |
| CN112875686A (en) * | 2021-02-04 | 2021-06-01 | 上海交通大学 | Preparation method of porous graphene based on sodium hypochlorite |
| CN113620273B (en) * | 2021-08-13 | 2023-04-25 | 苏州大学 | Carbon-based metal-free functional quantum dot and preparation and application thereof |
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| CN102336404A (en) * | 2011-07-19 | 2012-02-01 | 上海交通大学 | Preparation method of graphene oxide quantum dot based on photocatalytic oxidation |
| WO2014179708A1 (en) * | 2013-05-02 | 2014-11-06 | William Marsh Rice University | Methods of producing graphene quantum dots from coal and coke |
| CN104556004A (en) * | 2014-12-26 | 2015-04-29 | 西北大学 | Preparation method of controlled fluorescent graphene quantum dot |
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| CN102336404A (en) * | 2011-07-19 | 2012-02-01 | 上海交通大学 | Preparation method of graphene oxide quantum dot based on photocatalytic oxidation |
| WO2014179708A1 (en) * | 2013-05-02 | 2014-11-06 | William Marsh Rice University | Methods of producing graphene quantum dots from coal and coke |
| CN104556004A (en) * | 2014-12-26 | 2015-04-29 | 西北大学 | Preparation method of controlled fluorescent graphene quantum dot |
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