CN109354014A - A kind of graphitized carbon quantum dot and preparation method thereof - Google Patents
A kind of graphitized carbon quantum dot and preparation method thereof Download PDFInfo
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- CN109354014A CN109354014A CN201811453167.8A CN201811453167A CN109354014A CN 109354014 A CN109354014 A CN 109354014A CN 201811453167 A CN201811453167 A CN 201811453167A CN 109354014 A CN109354014 A CN 109354014A
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- quantum dot
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/205—Preparation
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a kind of graphitized carbon quantum dot and preparation method thereof, this method is that Super P powder is dispersed in concentrated nitric acid/concentrated sulfuric acid mixed acid to carry out back flow reaction, reaction product successively pass through purification process and reduction treatment to get.This method is easy to operate, and carbon quantum dot yield is high, low in cost, it is easy to accomplish large-scale production, and the carbon quantum dot prepared (being less than 10nm) of uniform size, electric conductivity are preferable, are expected to the conductive agent as technical grade energy storage electrode material.
Description
Technical field
The present invention relates to a kind of carbon quantum dot, in particular to a kind of graphitized carbon quantum dot further relates to utilize Super P high
The method that yield prepares graphitized carbon quantum dot belongs to carbon quantum dot preparation technical field.
Background technique
Carbon quantum dot (size is usually less than 10nm) is as a kind of novel zero dimension carbon material in recent years by world wide
Interior extensive concern, since it is with some unique properties such as quantum size effect and Dielectric confinement effect, in fluorescence, biology
Medicine, bio-imaging, sensing, photocatalysis, optical device and energy conversion show tempting prospect with storage art.?
It 2013, has been reported that using carbon quantum dot and the compound building composite material of ruthenic oxide as electrode material for super capacitor
[Energy Environ.Sci., 2013,6,3665-3675], compared to pure ruthenic oxide, which realizes enhancing
Capacitive property.From then on, carbon quantum dot is used for supercapacitor, lithium (sodium) ion battery, fuel cell and solar-electricity
The report in pond gradually increases.However the usable carbon quantum dot of storage currently prepared is primarily present that low yield, conductivity be not high to ask
Topic, limits its actual application.
Currently, it is prepared for high conductive graphitized carbon quantum dot by using chemical oxidization method in the prior art, but
It is its yield less than 20% [Energy Environ.Sci., 2013,6,3665-3675；J.Mater.Chem.A,2015,
3,866-877]；For another example, react to obtain the carbon quantum dot of high yield with highly basic using organic aldehyde compound, but its conduction
Property not high [Adv.Mater.2015,27,7861-7866], limits it in the practical application of energy storage field.
Summary of the invention
For the problems such as there are low yield and low conductivity by chemical method preparation carbon quantum dot in the prior art, this hair
Bright purpose is to be to provide a kind of method of graphitized carbon quantum dot that high yield preparation electrical conductance is excellent, and this method is simple,
It is at low cost, be conducive to be mass produced.
Second object of the present invention is to be to provide a kind of conductive good graphitized carbon quantum dot, the graphitization
Carbon quantum dot is expected to be applied to technical grade energy storage electrode material as conductive agent.
The present invention provides a kind of method that high yield prepares graphitized carbon quantum dot, this method is by Super P powder
It is dispersed in concentrated nitric acid/concentrated sulfuric acid mixed acid and carries out back flow reaction, reaction product successively passes through purification process and reduction treatment, i.e.,
?.
Preferred scheme, the concentrated nitric acid/concentrated sulfuric acid mixed acid are (0.1~1) by concentrated nitric acid and the concentrated sulfuric acid by volume:
1 composition.Concentrated nitric acid and concentrated nitric acid of the invention is common technical grade marketable material.Compared to use single acid, mixed acid by
It is stronger to Super P powder etching power in its stronger oxidisability, thus lead to higher graphitized carbon quantum dot yield.
Preferred scheme, the temperature of the back flow reaction are 60 DEG C~140 DEG C, and the time is 6h~48h.
Preferred scheme, the purification process include neutralization, filtering, dialysis and drying steps.Wherein, N-process is normal
The alkali neutralization process of rule is neutralized to pH as neutrality.
Preferred scheme, the dialysis use molecular cut off for the bag filter of 500Da~14000Da, and dialysis time is
12h~120h.
Preferred scheme, it is described dry using air drying, vacuum drying or freeze-drying.
Preferred scheme, the reduction treatment condition: in hydrogen and inert gas gaseous mixture, at 200 DEG C~1000 DEG C
At a temperature of, restore 1h~10h.Inert atmosphere such as argon gas.In general the volume ratio of hydrogen controls below 20%.Use hydrogen
The main purpose that gas and inert gas mixed gas carry out reduction treatment is to further decrease the oxygen-containing of the carbon quantum dot of generation
Its degree of graphitization improves in functional group.
Super P powder of the invention is common technical grade Super P powder, Average Particle Diameters 50nm.
The present invention is by Super P powder through ultrasonic disperse in concentrated nitric acid/concentrated sulfuric acid mixed acid.The frequency of ultrasonic disperse
For 30~50kHz, power is 80~120W, and ultrasonic time is 0.5~5h.It is former to be conducive to Super P powder by ultrasonic disperse
Material is sufficiently mixed with mixed acid, improves reaction efficiency.
The present invention also provides a kind of graphitized carbon quantum dots, are prepared by the above method.
Preferred scheme, the size of the graphitized carbon quantum dot is within the scope of 1~10nm.
Technical solution of the present invention bring advantageous effects compared with the prior art:
Technical solution of the present invention uses technical grade Super P powder to prepare carbon quantum dot by acid etching processes for the first time, system
Standby is graphited carbon quantum dot, has good electric conductivity, and the yield of the carbon quantum dot of this method preparation is much higher than it
His method, is conducive to the industrialized production and application of carbon quantum dot.
Technical solution of the present invention preparation process is simple, and raw material is commercially available conventional raw material, and reaction condition is mild, is conducive to work
Industry metaplasia produces.
Detailed description of the invention
[Fig. 1] is the solid powder photo of obtained carbon quantum dot in the embodiment of the present invention 1；
[Fig. 2] is the aqueous solution photo of obtained carbon quantum dot in the embodiment of the present invention 1；
[Fig. 3] is the XRD diagram of obtained carbon quantum dot in the embodiment of the present invention 1；
[Fig. 4] is the Raman figure of obtained carbon quantum dot in the embodiment of the present invention 1；
[Fig. 5] is the XPS figure of obtained carbon quantum dot in the embodiment of the present invention 1；
[Fig. 6] is the transmission electron microscope picture of obtained carbon quantum dot in the embodiment of the present invention 1.
Specific embodiment
Following embodiment is the further description to the content of present invention, rather than limits claim of the invention
Protection scope.
Embodiment 1:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:3) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 110 DEG C at a temperature of flow back for 24 hours；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain graphitized carbon quantum dot
Powder, carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.Fig. 1 is carbon amounts
The solid powder photo of son point, can be obtained the powder of 0.51g dark brown after obtained carbon quantum dot is freeze-dried.Fig. 2 is carbon
The aqueous solution photo of quantum dot, obtained carbon quantum dot is soluble easily in water, and still deposit-free after the placement several months.Fig. 3 is carbon
The XRD diagram of quantum dot, obtained carbon quantum dot is amorphous structure as we know from the figure.Fig. 4 is that the Raman of carbon quantum dot schemes,
In 1349 and 1572cm known in figure-1The peak D and the peak G at place are two characteristic peaks of carbon quantum dot.Fig. 5 is the XPS of carbon quantum dot
Scheme, the peak known in figure at 284.8eV corresponds to graphited C-C key, and the peak at 286.5,288.4 and 289.2eV then divides
Not Dui Yingyu C-O, C=O and O-C=O key, this shows that a certain number of oxygen-containing functions are contained on prepared carbon quantum dot surface
Group.Fig. 6 is the transmission electron microscope picture of carbon quantum dot, it can be seen that prepared carbon quantum dot size is more uniform, diameter be 5~
8nm, and its observed lattice fringe spacing is 0.215nm from illustration, belongs to (100) crystal face of graphite, this shows made
It is graphited carbon quantum dot for what is gone out.
Comparative example 1
By the Super P powder of technical grade and concentrated nitric acid (6mol L-1) flow back 48h at a temperature of 110 DEG C of mixing, product warp
The graphitized carbon quantum dot of 10% yield is obtained after crossing purification, dialysis and drying.
Comparative example 2
By the Super P powder of technical grade and concentrated nitric acid (12mol L-1) flow back 48h at a temperature of 110 DEG C of mixing, product
The graphitized carbon quantum dot of 18% yield is obtained after purification, dialysis and drying.
Embodiment 2:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:3) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 60 DEG C at a temperature of flow back for 24 hours；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.32g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Embodiment 3:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:3) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 80 DEG C at a temperature of flow back for 24 hours；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.41g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Embodiment 4:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:3) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 110 DEG C at a temperature of flow back 48h；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.51g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Embodiment 5:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:3) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 140 DEG C at a temperature of flow back 48h；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.51g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Embodiment 6:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:1) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 110 DEG C at a temperature of flow back 72h；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.42g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Embodiment 7:
It is the Super P conductive agent powder and concentrated nitric acid and the concentrated sulfuric acid (v/v, 1:10) of 50nm technical grade by 1g granular size
Mixing, ultrasonic 1h (100W, 40kHz), then 110 DEG C at a temperature of flow back for 24 hours；The mixed solution that will be obtained after natural cooling
It is neutralized with natrium carbonicum calcinatum, controls pH value 7.0 or so, carbon quantum dot solution is then obtained by filtration, then using retention molecule
The bag filter dialysis 72h that amount is 1000Da；Finally acquired solution after dialysis is freeze-dried to obtain 0.51g graphitization carbon amounts
Son puts powder, and carbon quantum dot solid powder can be obtained in thermal reduction 2h in hydrogen/argon gas gaseous mixture at further 500 DEG C.
Claims (9)
1. a kind of method that high yield prepares graphitized carbon quantum dot, it is characterised in that: Super P powder is dispersed to dense nitre
Carry out back flow reaction in acid/concentrated sulfuric acid mixed acid, reaction product successively pass through purification process and reduction treatment to get.
2. a kind of method that high yield prepares graphitized carbon quantum dot according to claim 1, it is characterised in that: the dense nitre
Acid/concentrated sulfuric acid mixed acid is (0.1~1) by concentrated nitric acid and the concentrated sulfuric acid by volume: 1 forms.
3. the method that a kind of high yield according to claim 1 or claim 2 prepares graphitized carbon quantum dot, it is characterised in that: described
The temperature of back flow reaction is 60 DEG C~140 DEG C, and the time is 6h~48h.
4. a kind of method that high yield prepares graphitized carbon quantum dot according to claim 1, it is characterised in that: the purifying
Processing includes neutralization, filtering, dialysis and drying steps.
5. the method that a kind of high yield according to claim 4 prepares graphitized carbon quantum dot, it is characterised in that: described
Analysis uses molecular cut off for the bag filter of 500Da~14000Da, and dialysis time is 12h~120h.
6. the method that a kind of high yield according to claim 1 prepares graphitized carbon quantum dot, it is characterised in that: described dry
It is dry to use air drying, vacuum drying or freeze-drying.
7. the method that a kind of high yield according to claim 1 prepares graphitized carbon quantum dot, it is characterised in that: described to go back
Former treatment conditions: in hydrogen and inert gas gaseous mixture, at a temperature of 200 DEG C~1000 DEG C, 1h~10h is restored.
8. a kind of graphitized carbon quantum dot, it is characterised in that: be prepared by any one of claim 1~7 method.
9. a kind of graphitized carbon quantum dot according to claim 8, it is characterised in that: the ruler of the graphitized carbon quantum dot
It is very little within the scope of 1~10nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534745A (en) * | 2019-08-07 | 2019-12-03 | 合肥国轩高科动力能源有限公司 | A kind of carbon quantum dot/SP combined conductive agent and preparation method thereof, application |
| CN113181906A (en) * | 2021-04-23 | 2021-07-30 | 西安交通大学 | Pt @ CDs composite nano material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106573778A (en) * | 2014-06-19 | 2017-04-19 | 威廉马歇莱思大学 | Bandgap engineering of carbon quantum dots |
| CN108467028A (en) * | 2018-04-26 | 2018-08-31 | 上海大学 | The preparation method and application of intelligent graphene quantum dot cluster |
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- 2018-11-30 CN CN201811453167.8A patent/CN109354014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106573778A (en) * | 2014-06-19 | 2017-04-19 | 威廉马歇莱思大学 | Bandgap engineering of carbon quantum dots |
| CN108467028A (en) * | 2018-04-26 | 2018-08-31 | 上海大学 | The preparation method and application of intelligent graphene quantum dot cluster |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534745A (en) * | 2019-08-07 | 2019-12-03 | 合肥国轩高科动力能源有限公司 | A kind of carbon quantum dot/SP combined conductive agent and preparation method thereof, application |
| CN113181906A (en) * | 2021-04-23 | 2021-07-30 | 西安交通大学 | Pt @ CDs composite nano material and preparation method thereof |
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