CN105948021B - The method that nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method - Google Patents
The method that nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method Download PDFInfo
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Abstract
The method that the present invention prepares nitrogen-doped graphene quantum dot using high-energy electron beam irradiation method, specific implementation step are：Treatment of Carbon will be heated to reflux with the concentrated sulfuric acid and concentrated nitric acid（CF）, pure common graphite alkene quantum dot is obtained after processing（GQDs）Aqueous solution；By GQDs aqueous solutions and a certain proportion of nitrogen, nitrogen dimethylformamide（DMF）Mixing ultrasound, and the deoxygenation sealing of drum nitrogen；The electron beam irradiation for carrying out doses is sent to again；Most pure N doping is obtained through deionized water dialysis treatment afterwards and issue the graphene quantum dot aqueous solution of white fluorescent in 365 nanometers of ultra violet lamps, be freeze-dried to obtain the nitrogen-doped graphene quantum dot of golden yellow powder（N‑GQDs）.Process of the present invention is simple, easy to operate, and can continuously start shooting irradiation, therefore can carry out large-scale production.
Description
Technical field
It the present invention relates to the use of the method that high-energy electron beam irradiation method prepares nitrogen-doped graphene quantum dot.
Background technology
It was by mechanically pulling off method by Novoselov and two people of Geim since 2004 and mono-layer graphite has been isolated from graphite
Since alkene, graphene has been carried out largely studying since its unique property causes researchers' keen interest,
Substantial amounts of data is obtained as a result, simultaneously having generated many application industries.It is adulterated in graphene nano sheet of material
Its hetero atom can change its electricity, optics and chemical reactivity etc..Since nitrogen-doped graphene nano material is with special
Light, electricity and chemical property, they have been widely used in biomarker, ultracapacitor, ion transducer, electro-catalysis
The fields such as reaction and hydrogen storage.
There are many method for preparing nitrogen-doped graphene nano material point, such as（1）By electrochemical method, with tetrabutylammonium
Perchloric acid（TBAP）Acetonitrile solution as electrolyte, the graphene film that is obtained with electronation graphene oxide and after filtering
For working electrode, cyclical voltage scanning is carried out, obtains the nitrogenous graphene quantum dot that N/C ratios are 4.3%；（2）Pass through chemical gaseous phase
Sedimentation（CVD）, in ammonia spirit, using ethylene and hydrogen as source of the gas, the graphite of pyridine N doping is prepared on copper sheet
Alkene quantum dot；（3）By heat treating process, the graphene oxide for having given pace to flow through ammonia, system are heated with certain heating rate
It is standby go out N doping graphene oxide；（4）Using ultrasonic method, it is laggard that the graphene after thermal reduction and hydrazine hydrate are added in into deionized water
Row heating ultrasound prepares the graphene of N doping.But most of method manufacturing cost is still excessively high at this stage, environment is not friendly
It is good, process conditions complexity be also required to it is further perfect, with a certain distance from being produced on a large scale still and having.High-energy electron beam irradiation method master
If the ionising radiation that this special medium generates using high-power electron beam makes hydrone free radical, and generates a large amount of hydrations
Electronics, these free radicals and aqueous electron and high-power electron beam can make a small amount of organic solvent nitrogen, nitrogen-dimethylformamide
（DMF）Free radical or ionization and graphene nano sheet of material is made to generate defect, and these free radicals or aqueous electron
Then may be with being chemically reacted at site the defects of graphene nano sheet of material, it finally may reduced graphene nanometer material
Some functional groups on tablet layer generate some new functional groups or even direct part changes graphene nano material piece
The structure of the big π rings of layer, so as to generate and the former graphene nano sheet of material structure new graphene nano that great changes have taken place
Material, also Just because of this, so its aqueous solution is not had issued under 360 nanometers of ultra violet lamps with former faint yellow fluorescence completely not
Same white fluorescent, and fluorescence quantum yield also greatly increases.Widely applied energy-rich radiation master in industry at present
Refer to high-power electron beam and gamma-rays.Gamma-rays is strong with penetrability, but dosage rate is generally too small, and time cost is too high,
So the high-power electron beam with heavy dose of rate is widely used in many fields.High-power electron beam this special treatment method is then
It has the following advantages：（1）It is easy to operate easy to control：By electron-beam accelerator operation console can simple operations electron-beam accelerator be
It is no how long to need to generate high-power electron beam and how much dose rate and irradiation；（2）Low cost：Electron-beam accelerator power leads to
Often only tens kilowatts, operating cost is low compared with general chemistry process；（3）It is environmental-friendly：It is smelly except generating in the process of running
Outside oxygen, the toxic pollutant of any hostile environment is not generated, and the electron beam irradiation generated in the process to start has preferable shielding
Safeguard measure；（4）Scale operation production：Can continuously be started shooting operation large-scale production.
The content of the invention
It is an object of the invention to provide a kind of nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method
Method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of method that nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method, it is characterised in that this method
Concretely comprise the following steps：
A. carbon fiber is immersed in nitration mixture, when room temperature ultrasound 1~2 is small after, be heated to reflux 18~36 it is small when, it is described mixed
Acid presses 3 for 98% concentrated sulfuric acid and 63% concentrated nitric acid:1 volume ratio mixes；Reaction terminates after being cooled to room temperature, and reaction solution is fallen
In the deionized water for entering 5-10 times of nitration mixture volume, then with molecular cut off be 3500 bag filter deionized water dialyse 5 days,
Obtain the pure graphene quantum dot GQDs aqueous solutions that faint yellow fluorescence is issued in 365 nanometers of ultra violet lamps；
B. GQDs solution obtained by step a is configured to the GQDs solution that concentration is 0.5~1mg/ml, by nitrogen, nitrogen-dimethyl
Formamide is configured to the nitrogen of concentration of volume percent 5%~95%, nitrogen-dimethylformamide in water；Two kinds of solution are mixed
Room temperature ultrasound 10~30 minutes afterwards, are poured into polythene film bag, then keep up nitrogen to discharge large quantity of air, last rapid heat-sealing
Bag；It is required that bag film tiling rear solution thickness may not exceed 1 centimetre；
C. the polythene film bag tiling that solution is housed in step b is placed in used in electron accelerator irradiation on conveyer belt,
At room temperature 280~560 kilograys are irradiated in the case where beam intensity is the electron beam of 8 milliamperes；
D. the bag filter deionized water that the solution molecular cut off after being irradiated in step c is 1000 is dialysed 5 days, obtained
To pure nitrogen-doped graphene quantum dot aqueous solution, nitrogen-doped graphene quantum dot is obtained after freeze-drying.
Using high-energy electron beam irradiation method in the presence of a small amount of organic solvent DMF to common GQDs aqueous solutions at
Reason, has obtained the stone for the good aqueous solubility that white fluorescent is issued doped with a large amount of nitrogens and in 360 nanometers of ultra violet lamps
Black alkene quantum dot N-GQDs.Process of the present invention is simple, easy to operate, environmental-friendly, low cost, easy to control, and can be continuous
Large-scale production.
Description of the drawings
Fig. 1 is the electromicroscopic photograph of sample one in the embodiment of the present invention one.
Fig. 2 is electromicroscopic photograph in sample two in the embodiment of the present invention one.
Specific embodiment
Embodiment one：
(1) by 300 milligrams of carbon fibers（carbonfibers,CF）Pour into nitration mixture（60 milliliter of 98% concentrated sulfuric acid and 20 milliliters
63% concentrated nitric acid）In, room temperature ultrasound 2 it is small when after be heated to reflux at 80 degrees celsius 24 it is small when.Reaction terminates to be cooled to room temperature rear molten
It dialyses 5 days, obtains pure in 200 ml deionized waters, then with the bag filter deionized water that molecular cut off is 3500
The GQDs aqueous solutions of faint yellow fluorescence are issued in 365 nanometers of ultra violet lamps.
(2) with the GQDs solution in a, it is 1 milligram every milliliter to prepare GQDs concentration, and containing n,N-Dimethylformamide
（DMF）Volume fraction is 5% aqueous solution, and room temperature ultrasound is poured into after 30 minutes in clean polythene film bag, then keeps up nitrogen
To discharge large quantity of air, last rapid heat-sealing bag.It is required that bag film tiling rear solution thickness may not exceed 1 centimetre, as far as possible
It is thinner.
(3) the polythene film bag tiling that solution is housed in b is placed in used in electron accelerator irradiation on conveyer belt, room temperature
Under beam intensity for 8 milliamperes electron beam under irradiate 560 kilograys.
(4) the bag filter deionized water that the aqueous solution molecular cut off after being irradiated in c is 1000 is dialysed 5 days, obtained
To pure nitrogen-doped graphene quantum dot（N-doped graphene quantum dots, N-GQDs）Aqueous solution, freezing
The N doping of golden yellow powder can be obtained after drying and issues the graphene amount of white fluorescent in 365 nanometers of ultra violet lamps
Sub- point N-GQDs.
Claims (1)
- A kind of 1. method that nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method, it is characterised in that this method It concretely comprises the following steps：A. carbon fiber is immersed in nitration mixture, when room temperature ultrasound 1~2 is small after, be heated to reflux 18~36 it is small when, the nitration mixture is 98% concentrated sulfuric acid and 63% concentrated nitric acid press 3:1 volume ratio mixes；Reaction terminates after being cooled to room temperature, and reaction solution is poured into 5- In the deionized water of 10 times of nitration mixture volumes, then with molecular cut off be 3500 bag filter deionized water dialyse 5 days, obtain The pure graphene quantum dot GQDs aqueous solutions that faint yellow fluorescence is issued in 365 nanometers of ultra violet lamps；B. GQDs solution obtained by step a is configured to the GQDs solution that concentration is 0.5~1mg/mL, by nitrogen, nitrogen-dimethyl formyl Amine is configured to the nitrogen of concentration of volume percent 5%~95%, nitrogen-dimethylformamide in water；Two kinds of solution are mixed into rear chamber Warm ultrasound 10~30 minutes, is poured into polythene film bag, then keeps up nitrogen to discharge large quantity of air, last rapid heat-sealing bag； It is required that bag film tiling rear solution thickness may not exceed 1 centimetre；C. the polythene film bag tiling that solution is housed in step b is placed in used in electron accelerator irradiation on conveyer belt, room temperature Under beam intensity for 8 milliamperes electron beam under irradiate 280~560 kilograys；D. the bag filter deionized water that the solution molecular cut off after being irradiated in step c is 1000 is dialysed 5 days, obtained pure Net nitrogen-doped graphene quantum dot aqueous solution obtains nitrogen-doped graphene quantum dot after freeze-drying.
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| CN106906451B (en) * | 2017-01-06 | 2019-06-11 | 四川大学 | A kind of electron irradiation preparation method of film surface aluminium oxide quantum dot |
| CN107252416A (en) * | 2017-05-08 | 2017-10-17 | 上海大学 | Method for preparing lipidosome of the one kind containing irradiation graphene quantum dot (IGQDs) |
| CN107213116A (en) * | 2017-05-08 | 2017-09-29 | 上海大学 | It is a kind of to improve the method that liposome carries doxorubicin hydrochloride content |
| CN108359451A (en) * | 2018-01-12 | 2018-08-03 | 湖北民族学院 | Graphene quantum dot and preparation method thereof |
| CN111285356B (en) * | 2018-12-10 | 2022-09-09 | 天津工业大学 | Preparation method of small-size graphene quantum dots |
| CN109898002B (en) * | 2019-04-30 | 2020-10-27 | 三桥惠(佛山)新材料有限公司 | Magnesium-based hydrogen storage alloy and preparation method thereof |
| CN113066976B (en) * | 2021-03-19 | 2023-03-17 | 中国科学院上海应用物理研究所 | Application of nitrogen-doped carbon nanotube in lithium ion battery cathode material |
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| CN104098093A (en) * | 2014-08-01 | 2014-10-15 | 天津工业大学 | Method for preparing fluorinated graphene based on gama ray irradiation |
| CN105460919A (en) * | 2014-08-29 | 2016-04-06 | 中国科学院过程工程研究所 | Ozonation-based method for preparing graphene quantum dots |
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|---|---|---|---|---|
| CN104098093A (en) * | 2014-08-01 | 2014-10-15 | 天津工业大学 | Method for preparing fluorinated graphene based on gama ray irradiation |
| CN105460919A (en) * | 2014-08-29 | 2016-04-06 | 中国科学院过程工程研究所 | Ozonation-based method for preparing graphene quantum dots |
Non-Patent Citations (1)
| Title |
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| 石墨烯量子点的制备与电子束辐照发光;杨杏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160215(第2期);17页倒数第3行至第倒数第1行，18页倒数第10行至倒数第6行，28页倒数第12行至倒数第4行，35页倒数第10行至倒数第9行 * |
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