CN102992311A - Method for preparing graphene quantum dots through carbon nano tube - Google Patents
Method for preparing graphene quantum dots through carbon nano tube Download PDFInfo
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- CN102992311A CN102992311A CN2012105250339A CN201210525033A CN102992311A CN 102992311 A CN102992311 A CN 102992311A CN 2012105250339 A CN2012105250339 A CN 2012105250339A CN 201210525033 A CN201210525033 A CN 201210525033A CN 102992311 A CN102992311 A CN 102992311A
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Abstract
The invention discloses a method for preparing graphene quantum dots through a carbon nano tube. The method comprises the following steps of: adding a mixed solution of nitric acid and sulfuric acid into the carbon nano tube, heating in a water bath, magnetically stirring, cooling to room temperature, diluting by using distilled water, regulating the pH value, performing dialysis and ultrafiltration centrifugation, and extracting through an organic solvent, so as to prepare the graphene quantum dots. The carbon nano tube which is diversified in growth modes and easy to control serves as a raw material, the graphene quantum dots are prepared through simple and controllable water bath heating and stirring operation; and the graphene quantum dot has the characteristics of good fluorescence effect, controllable fluorescence range, water solubility and the like, can be soluble with most of polymers through extraction and can be applied to the improvement of the device performance in photoelectric materials and devices.
Description
Technical field
The invention belongs to the preparing technical field of graphene quantum dot, be specifically related to a kind of method that is prepared graphene quantum dot by carbon nanotube.
Background technology
Graphene relies on its unique physics, chemistry, mechanical characteristics to become the upstart who gets most of the attention in material and the device application, but owing to itself be a kind of semi-metallic of zero band gap, and have bipolarity, therefore the application in photoelectron material is restricted.How can open being with of Graphene and make it become within the specific limits adjustable semi-conductor of band gap, become the research emphasis of photoelectron material and device scientific circles.
Experiment and theoretical investigation show that the relative graphene nanobelt of graphene quantum dot has more significant fringing effect and stronger quantum limitation effect.Graphene quantum dot also has low cytotoxicity, good water-soluble, stable fluorescence and excellent biocompatibility in addition, these so that graphene quantum dot have great application prospect at aspects such as photoelectric device, bio-sensing and imagings.
The investigator used the methods such as electron beam lithography, focused-ion-beam lithography to prepare graphene quantum dot in recent years, and these methods can only be as the preparation means of fundamental research, and its technique is loaded down with trivial details, and cost is expensive, and output is lower and be not suitable for batch production and use.In addition, from various carbon sources, method by solution " cutting " prepares in the research of graphene quantum dot, still exist in the preparation method that the difficult fluorescence that guarantees graphene quantum dot is controlled, particle diameter consistent and the problem such as chemical stability, the present invention solves these problems in these areas.
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Summary of the invention
The object of the present invention is to provide a kind of method that is prepared graphene quantum dot by carbon nanotube, the present invention adopts that growth pattern is various, the carbon nanotube of easy control is that raw material is prepared graphene quantum dot by simple controlled heating in water bath stirring operation, it has very the hyperfluorescenceCeng Yongminggaoyingguang effect and the fluorescence scope is controlled, with the characteristics such as water is miscible, through the extraction can with most of Polymers Miscibility, can be applicable in a lot of photoelectric materials and the device and improve device performance.
For achieving the above object, the present invention adopts following technical scheme:
A kind ofly prepare the method for graphene quantum dot by carbon nanotube, in carbon nanotube, add the mixing solutions of nitric acid and sulfuric acid, be cooled to room temperature after heating in water bath, the magnetic agitation, use distilled water diluting, regulate the pH value, dialysis and ultrafiltration are centrifugal, use organic solvent extraction, namely make graphene quantum dot.
Described carbon nanotube is single wall, double-walled or multi-walled carbon nano-tubes.
The molar ratio of nitric acid and sulfuric acid is 1:8 ~ 3:4 in the mixing solutions of described nitric acid and sulfuric acid, and the massfraction of water is 0.5 ~ 15%.
The volume ratio of the mixing solutions of the quality of described carbon nanotube and nitric acid and sulfuric acid is 2 ~ 6mg/mL.
Described water bath heating temperature is 80 ~ 150 ℃, and the time is 12 ~ 30 hours, and magnetic agitation power is 30 ~ 120W.
Described adjusting pH value adopts NaOH or sodium carbonate solution.
It is 2000 ~ 8000Da that molecular weight cut-off is adopted in described dialysis, and the dialysis time is 2 ~ 8 days.
The centrifugal employing molecular weight cut-off of described ultrafiltration is 2000 ~ 8000Da, and centrifugal rotational speed is 3000 ~ 7000 rev/mins, and the time is 30 ~ 60 minutes.
Described organic solvent is 1:1 ~ 5 with the volume ratio that is extracted liquid, and extraction time is 12 ~ 48 hours.
Described organic solvent is chlorobenzene.
Beneficial effect of the present invention is: the invention provides a kind of method that is prepared graphene quantum dot by carbon nanotube, the advantages such as that this preparation method has is simple to operate, condition is easily controlled, prepare fast, through the graphene quantum dot consistent size after the extraction, size distribution is even, has good fluorescent characteristic, can mix with numerous common polymer, be easy to be applied in the organic optoelectronic device.
Description of drawings
Fig. 1 is the schema that is prepared the method for graphene quantum dot by carbon nanotube provided by the invention.
Fig. 2 provided by the inventionly prepares the fluorescence spectrum figure of the graphene quantum dot that the method for graphene quantum dot makes by carbon nanotube, and excitation wavelength is respectively the UV-light of 330nm.
Fig. 3 is the chlorobenzene solution photo under fluorescent lamp and ultra violet lamp respectively after the method extraction that is prepared graphene quantum dot by carbon nanotube provided by the invention, and the left side is under the ultra violet lamp, and the right is the photo under the fluorescent lamp irradiation.Can find out that graphene quantum dot solution shows strong blue-fluorescence under ultra violet lamp, and shine next without obvious fluorescent emission at fluorescent lamp.
Embodiment
The below is described in detail the technical scheme in the embodiment of the invention.But described embodiment only is a part of embodiment of the present invention, is not limited to this.
Embodiment 1
(wherein the mass percentage concentration of concentrated nitric acid is 68% for caliber＜5nm, the mixing solutions of pipe range 5 ~ 15um) adding concentrated nitric acids and the vitriol oil, and the mass percentage concentration of the vitriol oil is 98%, and 1:3 is mixed to get with volume ratio to adopt the 0.030g double-walled carbon nano-tube.
After the heating in water bath magnetic agitation, water bath heating temperature is 100 ℃, and the time is 24 hours, and magnetic agitation power is 80W, is cooled to room temperature, dilutes with the distilled water of 2 times of volumes, adopts concentrated NaOH solution to regulate mixing solutions pH=8.
Adopting molecular weight cut-off is that the dialysis bag of 3000Da is processed the dialysis of gained solution, and the dialysis time is 5 days, during outside changing dialysis bag in 24 hours distilled water.Gained solution after the dialysis is carried out the centrifugal shrink of ultrafiltration, and the centrifugal employing molecular weight cut-off of ultrafiltration is 3000Da, and centrifuge speed is 6000 rev/mins, and centrifugation time is 40 minutes, obtains the graphene quantum dot aqueous dispersions.
Centrifugal gained solution is adopted the chlorobenzene extraction, and the volume ratio of extraction agent and the aqueous solution is 1:2, and time of repose is 24 hours, obtains the graphene quantum dot with blue-fluorescence effect.
The graphene quantum dot of the inventive method preparation has good dispersiveness and consistent particle size after extraction.Carry out optic test through fluorescence spectrophotometer, the result shows that quantum dot can produce very strong blue-fluorescence under ultraviolet lighting, show the Fluorescence behaviour relevant with excitation wavelength, in opto-electronic device and biosensor and bio-imaging, have great application prospect.
Embodiment 2
Change embodiment 1 Raw into the 0.030g multi-walled carbon nano-tubes, other conditions are constant, can obtain product similar to Example 1.
Embodiment 3
Water bath heating temperature among the embodiment 1 is controlled to be 90 ℃, and other conditions are constant, can obtain product similar to Example 1.
Embodiment 4
Heating in water bath among the embodiment 1 is changed to oil bath, and temperature is controlled to be 120 ℃, and other conditions are constant, can obtain product similar to Example 1.
Embodiment 5
Change the heating in water bath magnetic agitation time among the embodiment 1 into 18 hours, other conditions are constant, can obtain product similar to Example 1.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. method that is prepared graphene quantum dot by carbon nanotube, it is characterized in that: the mixing solutions that in carbon nanotube, adds nitric acid and sulfuric acid, be cooled to room temperature after heating in water bath, the magnetic agitation, use distilled water diluting, regulate the pH value, dialysis and ultrafiltration are centrifugal, use organic solvent extraction, namely make graphene quantum dot.
2. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: described carbon nanotube is single wall, double-walled or multi-walled carbon nano-tubes.
3. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: the molar ratio of nitric acid and sulfuric acid is 1:8 ~ 3:4 in the mixing solutions of described nitric acid and sulfuric acid, and the massfraction of water is 0.5 ~ 15%.
4. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: the volume ratio of the mixing solutions of the quality of described carbon nanotube and nitric acid and sulfuric acid is 2 ~ 6mg/mL.
5. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: described water bath heating temperature is 80 ~ 150 ℃, and the time is 12 ~ 30 hours, and magnetic agitation power is 30 ~ 120W.
6. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: described adjusting pH value adopts NaOH or sodium carbonate solution.
7. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: it is 2000 ~ 8000Da that molecular weight cut-off is adopted in described dialysis, and the dialysis time is 2 ~ 8 days.
8. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: the centrifugal employing molecular weight cut-off of described ultrafiltration is 2000 ~ 8000Da, and centrifugal rotational speed is 3000 ~ 7000 rev/mins, and the time is 30 ~ 60 minutes.
9. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: described organic solvent is 1:1 ~ 5 with the volume ratio that is extracted liquid, and extraction time is 12 ~ 48 hours.
10. according to claim 1ly prepare the method for graphene quantum dot by carbon nanotube, it is characterized in that: described organic solvent is chlorobenzene.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332675A (en) * | 2013-07-04 | 2013-10-02 | 上海交通大学 | Graphene quantum dot based method for synthesis of carbon nanotube by chemical vapor deposition |
| CN103708447A (en) * | 2013-12-27 | 2014-04-09 | 中国科学院上海微系统与信息技术研究所 | Method for purifying graphene oxide quantum dots |
| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微系统与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN104650862A (en) * | 2015-01-22 | 2015-05-27 | 南京邮电大学 | Preparation and applications of graphene quantum dots with white fluorescence emission properties |
| CN104762082A (en) * | 2015-02-28 | 2015-07-08 | 安徽师范大学 | Graphene quantum dot, preparation method thereof and urea detection method |
| CN104861967A (en) * | 2015-04-14 | 2015-08-26 | 中国工程物理研究院化工材料研究所 | Preparation method and application of nitrogen-doped graphene quantum dots |
| CN104944403A (en) * | 2014-03-24 | 2015-09-30 | 中国科学院兰州化学物理研究所 | Preparation method of water-soluble bi-colour fluorinated graphene quantum dot |
| CN106241772A (en) * | 2016-07-26 | 2016-12-21 | 中国科学院兰州化学物理研究所 | A kind of method utilizing biomass flue dust efficiently to prepare carbon quantum dot |
| CN108047472A (en) * | 2017-11-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of preparation method of the polymer composite film based on graphene quantum dot doping |
| TWI684567B (en) * | 2018-07-12 | 2020-02-11 | 國立中正大學 | Method for preparing graphene quantum dots |
| CN112520727A (en) * | 2020-10-14 | 2021-03-19 | 扬州大学 | Carbon nanotube prepared by taking graphene quantum dots as template and method thereof |
| CN112618570A (en) * | 2020-01-07 | 2021-04-09 | 武汉大学 | Preparation method of graphene quantum dots and application of graphene quantum dots in preparation of medicine for treating non-alcoholic fatty liver disease |
| CN113526607A (en) * | 2020-04-16 | 2021-10-22 | 中国环境科学研究院 | Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332675A (en) * | 2013-07-04 | 2013-10-02 | 上海交通大学 | Graphene quantum dot based method for synthesis of carbon nanotube by chemical vapor deposition |
| CN103332675B (en) * | 2013-07-04 | 2015-12-09 | 上海交通大学 | Based on the method for graphene quantum dot chemical vapour deposition synthesizing carbon nanotubes |
| CN103708447B (en) * | 2013-12-27 | 2015-11-18 | 中国科学院上海微系统与信息技术研究所 | The method of purification of graphene oxide quantum dot |
| CN103708447A (en) * | 2013-12-27 | 2014-04-09 | 中国科学院上海微系统与信息技术研究所 | Method for purifying graphene oxide quantum dots |
| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微系统与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN104045076B (en) * | 2014-01-17 | 2016-01-20 | 中国科学院上海微系统与信息技术研究所 | The preparation method of graphene oxide quantum dot |
| CN104944403B (en) * | 2014-03-24 | 2017-04-26 | 中国科学院兰州化学物理研究所 | Preparation method of water-soluble bi-colour fluorinated graphene quantum dot |
| CN104944403A (en) * | 2014-03-24 | 2015-09-30 | 中国科学院兰州化学物理研究所 | Preparation method of water-soluble bi-colour fluorinated graphene quantum dot |
| CN104650862A (en) * | 2015-01-22 | 2015-05-27 | 南京邮电大学 | Preparation and applications of graphene quantum dots with white fluorescence emission properties |
| CN104762082A (en) * | 2015-02-28 | 2015-07-08 | 安徽师范大学 | Graphene quantum dot, preparation method thereof and urea detection method |
| CN104861967A (en) * | 2015-04-14 | 2015-08-26 | 中国工程物理研究院化工材料研究所 | Preparation method and application of nitrogen-doped graphene quantum dots |
| CN106241772A (en) * | 2016-07-26 | 2016-12-21 | 中国科学院兰州化学物理研究所 | A kind of method utilizing biomass flue dust efficiently to prepare carbon quantum dot |
| CN108047472A (en) * | 2017-11-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of preparation method of the polymer composite film based on graphene quantum dot doping |
| TWI684567B (en) * | 2018-07-12 | 2020-02-11 | 國立中正大學 | Method for preparing graphene quantum dots |
| CN112618570A (en) * | 2020-01-07 | 2021-04-09 | 武汉大学 | Preparation method of graphene quantum dots and application of graphene quantum dots in preparation of medicine for treating non-alcoholic fatty liver disease |
| CN113526607A (en) * | 2020-04-16 | 2021-10-22 | 中国环境科学研究院 | Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application |
| CN112520727A (en) * | 2020-10-14 | 2021-03-19 | 扬州大学 | Carbon nanotube prepared by taking graphene quantum dots as template and method thereof |
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