CN108892131A - A kind of graphene quantum dot and preparation method thereof - Google Patents
A kind of graphene quantum dot and preparation method thereof Download PDFInfo
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- CN108892131A CN108892131A CN201811140848.9A CN201811140848A CN108892131A CN 108892131 A CN108892131 A CN 108892131A CN 201811140848 A CN201811140848 A CN 201811140848A CN 108892131 A CN108892131 A CN 108892131A
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Abstract
The invention discloses a kind of graphene quantum dots and preparation method thereof, and the preparation method comprises the following steps：(1) carbon black is taken to be placed in nitration mixture, batch type flows back to obtain mixed liquor, and the nitration mixture is that the concentrated sulfuric acid is mixed with concentrated nitric acid；(2) mixed liquor in step (1) is cooled to room temperature, the pH of the mixed liquor is adjusted to neutrality, after be acidified to pH=1, be made graphene quantum dot.Graphene quantum dot uniform particle diameter, the stabilization being prepared, and edge carboxyl steady in a long-term can be present in product, with good application prospect.
Description
Technical field
The present invention relates to quanta point material fields, more particularly, to a kind of graphene quantum dot and preparation method thereof.
Background technique
Graphene quantum dot (graphene quantum dots, GQD) is a kind of novel fluorescent material, is substantially
Single-layer graphene by two-dimensional at several nanometers to tens nanometers spatially stacks, have both graphene property and
Quantum effect, such as carrier mobility height, large specific surface area, mechanical performance is excellent, optics electrical properties are good, has quantum limit
Domain effect and boundary effect etc. are widely used in solar photoelectric, light emitting diode, various kinds of sensors, biological medicine detection etc.
Field is more and more paid attention to by researcher.
The particle diameter distribution of the graphene quantum dot prepared in the prior art is often wide, for example Chinese patent
A kind of preparation method of graphene quantum dot is disclosed in CN107758643A, the graphene quantum dot particle diameter distribution of preparation exists
Between 2~10nm, stringent device is required for certain pairs of particle sizes, quantum dot made from this method cannot be applied.
Summary of the invention
In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of graphene quantum dot and its
Preparation method, the graphene quantum dot particle diameter distribution being prepared is relatively narrow and edge carboxyl steady in a long-term can be present in
In product.
The technical solution adopted by the present invention is that：
The present invention provides a kind of preparation method of graphene quantum dot, includes the following steps：
(1) carbon black is taken to be placed in nitration mixture, batch type flows back to obtain mixed liquor, and the nitration mixture is the concentrated sulfuric acid and concentrated nitric acid
It mixes；
(2) mixed liquor in step (1) is cooled to room temperature, the pH of the mixed liquor is adjusted to neutrality, after be acidified to pH
=1~2, graphene quantum dot is made.
Preferably, intermittent in step (1) to be stirred at reflux specially：It is stirred at reflux at 125~135 DEG C 7~8 hours,
Then it reacts at room temperature 12~14 hours, this two process at least cycle alternation carries out primary.
Further, this two processes at least cycle alternation to reach 22 in 125~135 DEG C and at room temperature total reaction time~
24 hours.
Preferably, the concentrated sulfuric acid in step (1) nitration mixture：Volume ratio=2 of concentrated nitric acid：1.
Preferably, step (2) is added sodium bicarbonate and the pH of the mixed liquor is adjusted to neutrality.
Preferably, step (2) is added hydrochloric acid and is acidified.
It preferably, further include step (3)：The mixed liquor of step (2) is filtered, takes filtrate that solvent is added, it is rear to rotate
Solvent is removed, it is dry.
Further, filtering uses vacuum filtration in step (3).
Further, solvent described in step (3) is any one of acetone, methyl acetate.
The present invention also provides a kind of graphene quantum dots, are made by the preparation method of above-mentioned graphene quantum dot.
The beneficial effects of the invention are as follows：
The present invention provides a kind of preparation method of graphene quantum dot, the graphene quantum dot uniform particle diameter that is prepared,
Size is relatively small, is stirred at reflux operation wherein intermittent and is additionally favorable for carbon black after separating graphene quantum dot in mixed liquor H+
Under the action of complete edge carboxylated, subsequent acidification step to play Protect edge information there are a large amount of H+ in suspension system
The effect of carboxyl enables carboxyl is steady in a long-term to be present in graphene quantum dot, has preferable application prospect.
Detailed description of the invention
Fig. 1 is the TEM figure of graphene quantum dot in embodiment 1；
Fig. 2 is the fluorescence emission spectrogram of compound of graphene quantum dot in embodiment 1；
Fig. 3 is the fluorescence emission spectrogram of compound of graphene quantum dot in embodiment 2；
Fig. 4 is the fluorescence emission spectrogram of compound of graphene quantum dot in embodiment 3.
Specific embodiment
It is clearly and completely described below with reference to technical effect of the embodiment to design and generation of the invention, with
It is completely understood by the purpose of the present invention, feature and effect.Obviously, described embodiment is that a part of the invention is implemented
Example, rather than whole embodiments, based on the embodiment of the present invention, those skilled in the art is not before making the creative labor
Other embodiments obtained are put, the scope of protection of the invention is belonged to.
Embodiment 1
The present embodiment provides a kind of graphene quantum dots, are prepared from the following steps：A 2L large beaker is put in ice bath
It is placed on magnetic stirring apparatus to prepare nitration mixture, takes clean graduated cylinder to measure the 100mL concentrated sulfuric acid and 50mL concentrated nitric acid, concentrated nitric acid is fallen
After entering large beaker, then to large beaker it is poured slowly into the concentrated sulfuric acid, to be stirred continuously during this, be moved into after nitration mixture is cooled to room temperature
It in round-bottomed flask, weighs conductive black 2.5g the round-bottomed flask is added and form hybrid reaction system, at the external tail gas of reaction unit
Device is managed, tail gas absorption agent is the sodium hydroxide solution of 1mol/L.This system is stirred at reflux 8 hours at 130 DEG C, then at normal
It temperature lower stirring 12 hours, repeats this and is stirred at reflux process 3 times.Mixed system is moved into again in the 1L beaker being placed in ice bath and is stirred
It mixes, constantly adds sodium bicarbonate solid up to pH value=7, then be acidified to pH=1 with the hydrochloric acid of 1mol/L.Aperture is passed it through again
Size is that the stirring of 50mL acetone is added and is placed on Rotary Evaporators after 0.45 μm of teflon membrane filter is filtered by vacuum
Solvent and impurity are removed, is moved into vacuum oven after rotating for several times, obtains brownish red graphene within dry 30 minutes at 50 DEG C
Quantum dot powder amounts to 0.35g, yield 14%.The graphene quantum dot prepared is taken to be characterized, as shown in Figure 1, Fig. 1
Middle scale is 5nm, and the partial size of graphene quantum dot is between 3-5nm as seen from the figure, uniform particle diameter.Take the graphene prepared
Quantum dot, measure its fluorescence emission spectrum as shown in Fig. 2, 370nm wavelength exciting light irradiation under, the graphene quantum dot
Fluorescent emission peak position in 502nm.
The present embodiment uses intermittent reaction, and pyroprocess removes carbon black successively, and room temperature process makes the stone separated
Black alkene quantum dot H in mixed system+Under the action of complete edge carboxylated, repeat high temperature-available stabilization of room temperature process
Edge carboxylated graphene quantum dot.
Embodiment 2
A 2L large beaker is put in ice bath to be placed on magnetic stirring apparatus to prepare nitration mixture, and clean graduated cylinder is taken to measure 100mL
The concentrated sulfuric acid and 50mL concentrated nitric acid after concentrated nitric acid is poured into large beaker, then to large beaker are poured slowly into the concentrated sulfuric acid, during this otherwise
Disconnected stirring, moves into round-bottomed flask after nitration mixture is cooled to room temperature, and weighs conductive black 5g and round-bottomed flask formation mixing is added
Reaction system, the external exhaust gas processing device of reaction unit, tail gas absorption agent are the sodium hydroxide solution of 1mol/L.By this system in
It is stirred at reflux at 130 DEG C 8 hours, is stirred 12 hours under room temperature, repeat this and be stirred at reflux process 3 times.Again by mixed system
It moves into the 1L beaker being placed in ice bath and stirs, constantly add sodium bicarbonate solid up to pH value=7, then the hydrochloric acid with 1mol/L
It is acidified to pH=1.Passing it through pore size again is that after 0.45 μm of teflon membrane filter is filtered by vacuum, 70mL is added
Acetone stirring, which is placed on Rotary Evaporators, removes solvent and impurity, moves into vacuum oven after rotating for several times, at 50 DEG C
It obtains brownish red graphene quantum dot powder within dry 30 minutes, amounts to 0.45g, yield 9%.Take the graphene quantum prepared
Point measures its fluorescence emission spectrum as shown in figure 3, excitation wavelength is 370nm.
Embodiment 3
A 2L large beaker is put in ice bath to be placed on magnetic stirring apparatus to prepare nitration mixture, and clean graduated cylinder is taken to measure 200mL
The concentrated sulfuric acid and 100mL concentrated nitric acid after concentrated nitric acid is poured into large beaker, then to large beaker are poured slowly into the concentrated sulfuric acid, want during this
It is stirred continuously, is moved into round-bottomed flask after nitration mixture is cooled to room temperature, weigh conductive black 2.5g the round-bottomed flask is added and formed
Hybrid reaction system, the external exhaust gas processing device of reaction unit, tail gas absorption agent are the sodium hydroxide solution of 1mol/L.By this body
It lies at 130 DEG C and is stirred at reflux 8 hours, stirred 12 hours under room temperature, repeat this and be stirred at reflux process 3 times.It again will mixing
System is moved into the 1L beaker being placed in ice bath and is stirred, and constantly adds sodium bicarbonate solid up to pH value=7, then with 1mol/L's
Hydrochloric acid is acidified to pH=1.Passing it through pore size again is after 0.45 μm of teflon membrane filter is filtered by vacuum, to be added
The stirring of 50mL acetone, which is placed on Rotary Evaporators, removes solvent and impurity, moves into vacuum oven after rotating for several times, in 50
It obtains brownish red graphene quantum dot powder within dry 30 minutes at DEG C, amounts to 0.27g, yield 10.8%.Take the graphite prepared
Alkene quantum dot measures its fluorescence emission spectrum as shown in figure 4, excitation wavelength is 370nm.
Embodiment 4
The present embodiment provides a kind of graphene quantum dots, are prepared from the following steps：A 2L large beaker is put in ice bath
It is placed on magnetic stirring apparatus to prepare nitration mixture, takes clean graduated cylinder to measure the 100mL concentrated sulfuric acid and 50mL concentrated nitric acid, concentrated nitric acid is fallen
After entering large beaker, then to large beaker it is poured slowly into the concentrated sulfuric acid, to be stirred continuously during this, be moved into after nitration mixture is cooled to room temperature
It in round-bottomed flask, weighs conductive black 2.5g the round-bottomed flask is added and form hybrid reaction system, at the external tail gas of reaction unit
Device is managed, tail gas absorption agent is the sodium hydroxide solution of 1mol/L.This system is stirred at reflux 6 hours at 125 DEG C, then at normal
It temperature lower stirring 12 hours, repeats this and is stirred at reflux process 4 times.Mixed system is moved into again in the 1L beaker being placed in ice bath and is stirred
It mixes, constantly adds sodium bicarbonate solid up to pH value=7, then be acidified to pH=1~2 with the hydrochloric acid of 1mol/L, obtain containing stone
The solution of black alkene quantum dot.Passing it through pore size again is after 0.45 μm of teflon membrane filter is filtered by vacuum, to add
Enter the stirring of 50mL acetone and be placed on removal solvent and impurity on Rotary Evaporators, is moved into vacuum oven after rotating for several times, in
Obtain brownish red graphene quantum dot powder within dry 30 minutes at 50 DEG C.
Claims (10)
1. a kind of preparation method of graphene quantum dot, which is characterized in that include the following steps：
(1) carbon black is taken to be placed in nitration mixture, batch type flows back to obtain mixed liquor, and the nitration mixture is that the concentrated sulfuric acid is mixed with concentrated nitric acid
It forms；
(2) mixed liquor in step (1) is cooled to room temperature, the pH of the mixed liquor is adjusted to neutrality, after be acidified to pH=1~
2, graphene quantum dot is made.
2. the preparation method of graphene quantum dot according to claim 1, which is characterized in that intermittent in step (1) to stir
Mixing reflux is specially：It is stirred at reflux 10~12 hours, then reacts at room temperature 14~16 hours, this two process at 125~135 DEG C
At least cycle alternation carries out primary.
3. the preparation method of graphene quantum dot according to claim 2, which is characterized in that this two process at least recycles friendship
For to reaching 24 hours or more in 125~135 DEG C and at room temperature total reaction time.
4. the preparation method of graphene quantum dot according to claim 1-3, which is characterized in that step (1) is mixed
The concentrated sulfuric acid in acid：Volume ratio=2 of concentrated nitric acid：1.
5. the preparation method of graphene quantum dot according to claim 1-3, which is characterized in that step (2) adds
Enter sodium bicarbonate and the pH of the mixed liquor is adjusted to neutrality.
6. the preparation method of graphene quantum dot according to claim 1-3, which is characterized in that step (2) adds
Enter hydrochloric acid to be acidified.
7. the preparation method of graphene quantum dot according to claim 1-3, which is characterized in that further include step
(3)：The mixed liquor of step (2) is filtered, takes filtrate that solvent is added, solvent is evaporated off in back spin, dry.
8. the preparation method of graphene quantum dot according to claim 7, which is characterized in that filtering uses in step (3)
Vacuum filtration.
9. the preparation method of graphene quantum dot according to claim 7, which is characterized in that solvent described in step (3)
For any one of acetone, methyl acetate.
10. a kind of graphene quantum dot, which is characterized in that by the system of the described in any item graphene quantum dots of claim 1-9
Preparation Method is made.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112552902A (en) * | 2020-11-20 | 2021-03-26 | 扬州大学 | Graphene quantum dot assembly with foam structure and preparation method thereof |
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