CN104909356A - Graphene oxide and graphene oxide quantum dot solvothermal controllable preparation method and use thereof - Google Patents
Graphene oxide and graphene oxide quantum dot solvothermal controllable preparation method and use thereof Download PDFInfo
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- CN104909356A CN104909356A CN201510268945.6A CN201510268945A CN104909356A CN 104909356 A CN104909356 A CN 104909356A CN 201510268945 A CN201510268945 A CN 201510268945A CN 104909356 A CN104909356 A CN 104909356A
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Abstract
The invention belongs to the technical field of nano-material preparation and concretely relates to a graphene oxide and graphene oxide quantum dot solvothermal controllable preparation method and a use thereof. The preparation method comprises that common graphite as a raw material is added with a certain amount of sulfuric acid and potassium permanganate, the mixture is stirred for some time, the mixed solution is added with nitric acid, the suspending liquid is transferred into a Teflon reactor, the mixture undergoes a solvothermal reaction, the reaction product flavescent transparent liquid is dispersed in deionized water, a certain amount of the solution is subjected to dialysis until pH is 7 so that the graphene oxide or graphene oxide quantum dot aqueous solution is obtained in a dialysis bag, and the aqueous solution is subjected to freeze drying so that graphene oxide or graphene oxide quantum dot powder is obtained. In preparation, the graphene oxide or graphene oxide quantum dot can be produced only by control of a reaction temperature and graphene oxide quantum dots with different particle sizes can be obtained by change of a ratio of graphite to potassium permanganate. The preparation method utilizes one-step solvothermal method, has simple operation and after-treatment processes, and has a short period, a low cost, no toxicity and no pollution. The produced material can be widely used in fields of photoelectric devices, anti-counterfeiting, biomolecule fluorescence labeling and bioimaging.
Description
Technical field
The present invention relates to nano material preparation technology
Technical background
Carbon is element the abundantest on the earth, it with various fractions distribution in physical environment.Due to its wide material sources, with low cost, carbon-based material is once having occurred into study hotspot.Graphene is found in 2004, and have excellent electrical properties, physical strength and thermostability, its discovery creates very large impact to Science and Technology.The presoma that graphene oxide is considered to chemistry, Graphene is prepared in thermal reduction.Graphene oxide is reacted by strong oxidizer and graphite usually to be prepared, and there are many oxy radicals on its surface, makes it have the character of some uniquenesses and water-soluble, has very large potential using value.But general preparation method's step of graphene oxide is more, consuming time longer, is unfavorable for extensive preparations and applicatio.
Graphene quantum dot, as the novel quantum dot of one, has attracted a large amount of investigators.Because of its significant quantum confinement and fringing effect, present a large amount of novel physics, chemical property.Comprising: hypotoxicity, solvability, chemical stability, light stability etc. make it in opto-electronic device, senser element and bio-imaging etc., have very large application potential.The method preparing graphene quantum dot at present can be divided into two classes: method from top to bottom and from bottom to top.Because the advantages such as method abundant raw material from top to bottom, operation be relatively simple are widely used.In addition, graphene quantum dot prepared by this method contains oxy radical at edge usually, and these groups contribute to improving its solvability, realizing multifunction and surface passivation.But this type of preparation method also also exists deficiency at present, as needed special instrument, yield poorly, the low and non-selectivity chemical shearing process of efficiency is unfavorable for controlling pattern and size.
For above problem, prepare graphene oxide by simple method efficiently and the controlled graphene oxide quantum dot tool of appearance and size has very important significance.
Summary of the invention
For preparing now, graphene oxide process is loaded down with trivial details, the problems such as graphene quantum dot preparation efficiency is low, appearance and size is wayward, the object of the invention is by a step solvent thermal reaction, graphene oxide or graphene oxide quantum dot is obtained, by changing graphite and potassium permanganate accurate controlled oxidization graphene quantum dot size by control temperature.The method is simple to operate, and consuming time short, controlled variable is few, and does not need complicated aftertreatment, and cost is low, can prepare in a large number, and business use value is high.
Solvent thermal prepares the method for graphene oxide and graphene quantum dot, and step is as follows:
Step 1: by Graphite Powder 99 and potassium permanganate (KMnO
4) put into beaker; Add sulfuric acid (H
2sO
4) and nitric acid (HNO
3); Stir 0.5-1 hour.Described graphite and potassium permanganate (KMnO
4) mass ratio be 4: 3-1: 4, sulfuric acid (H
2sO
4) and nitric acid (HNO
3) volume ratio be 9: 1-3: 1.
Step 2: above reactant being all transferred to volume is in the tetrafluoroethylene reactor of 25-250mL, reacts in an oven.Described temperature of reaction is 120-180 DEG C, and the reaction times is 0.5-3 hour.
Step 3: after question response completes, gained Solution Dispersion is stand-by in 30-300mL deionized water;
Step 4: get a certain amount of dialysis tubing that adds and water is dialysed to pH as neutral.The molecular weight cut-off of described dialysis tubing is 1000-3500Da.
Step 5: by the neutral aqueous solution lyophilize obtained, namely obtains graphene oxide or graphene oxide quantum dot powder.
Can predict, prepared graphene oxide and graphene quantum dot may be widely used in transmission ofenergy and biomarker, imaging.
Accompanying drawing explanation
A)-b in Fig. 1) transmission electron microscope photo of sample prepared by embodiment of the present invention 1-2;
A)-d in Fig. 2) transmission electron microscope photo of sample prepared by embodiment of the present invention 3-6;
(exciting light is interval from 330 to 510nm with 20nm for the emmission spectrum of Fig. 3 sample prepared by the embodiment of the present invention 2; In illustration, intensity is normalized intensity);
Fig. 4 sample prepared by the embodiment of the present invention 2 is done cell image (405nm excites) on HeLa cell;
Embodiment
Embodiment 1:
By mass ratio be 1: 3 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 130 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Get and a certain amount ofly join in the dialysis tubing of molecular weight cut-off 3500Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide powder.
Embodiment 2:
By mass ratio be 1: 3 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 160 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Get and a certain amount ofly join in the dialysis tubing of molecular weight cut-off 1000Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide quantum dot powder.
Embodiment 3;
By mass ratio be 4: 3 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 160 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Product after dispersion is joined in the dialysis tubing of molecular weight cut-off 1000Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide quantum dot powder.
Embodiment 4:
By mass ratio be 6: 5 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 160 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Product after dispersion is joined in the dialysis tubing of molecular weight cut-off 1000Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide quantum dot powder.
Embodiment 5:
By mass ratio be 5: 6 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 160 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Product after dispersion is joined in the dialysis tubing of molecular weight cut-off 1000Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide quantum dot powder.
Embodiment 6:
By mass ratio be 1: 2 Graphite Powder 99 and potassium permanganate put into beaker, add sulfuric acid and nitric acid that volume ratio is 3: 1, stir 30 minutes; Above reactant is all transferred in 25mL tetrafluoroethylene reactor, react 1.5 hours in the baking oven of 160 DEG C; After question response terminates, be all scattered in 50mL deionized water, stand-by; Product after dispersion is joined in the dialysis tubing of molecular weight cut-off 1000Da, dialysis 3-7 days; By the solution lyophilize in dialysis tubing, namely obtain graphene oxide quantum dot powder.
Claims (6)
1. a solvent thermal controllable method for preparing for graphene oxide and graphene oxide quantum dot, its feature comprises the following steps
A) Graphite Powder 99 and potassium permanganate are put into beaker, add the vitriol oil, stir;
B) continue to stir, add concentrated nitric acid;
C) suspension liquid obtained is transferred in polytetrafluoroethylkettle kettle inner bag, put into baking oven after sealing and react;
D) reaction obtains shallow yellow transparent solution after terminating, and dispersion in deionized water;
E) get a certain amount of dialysis to neutral, the neutral solution obtained after dialysis is graphene oxide or the graphene oxide quantum dot aqueous solution;
F) graphene oxide or graphene oxide quantum dot powder is obtained after lyophilize.
2. method according to claim 1, is characterized in that the mass ratio of graphite and potassium permanganate is 4: 3-1: 4, and the volume ratio of the vitriol oil and concentrated nitric acid is 9: 1-3: 1.
3. method according to claim 1, is characterized in that polytetrafluoroethylkettle kettle inner bag volume is 25-250mL.
4. method according to claim 1, is characterized in that temperature of reaction is at 120-180 DEG C, and the reaction times is: 0.5-3 hour.
5. method according to claim 1, it is characterized in that the molecular weight cut-off of dialysis tubing is 1000-3500Da, dialysis time is 3-7 days.
6. method according to claim 1, is characterized in that the drying mode adopted is lyophilize.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219528A (en) * | 2016-07-26 | 2016-12-14 | 湖南师范大学 | A kind of controlled method preparing graphene oxide and graphene oxide quantum dot |
| CN106348281A (en) * | 2015-07-13 | 2017-01-25 | 南京理工大学 | Method for preparing bifluorescence graphene quantum dots hydrothermally |
| CN107043104A (en) * | 2017-05-11 | 2017-08-15 | 桂林理工大学 | A kind of graphene quantum dot induces high nitrogen doped photo-reduction graphene oxide preparation method |
| CN107601466A (en) * | 2017-10-12 | 2018-01-19 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN110204991A (en) * | 2019-04-28 | 2019-09-06 | 西南石油大学 | A kind of efficient corrosion resisting h-BN/GO/ water-base epoxy composite material, preparation method and application |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633257A (en) * | 2012-05-04 | 2012-08-15 | 东南大学 | Method for synthesizing less than 10 nm of single-layer graphene quantum dot biological imaging agent |
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| CN102807209A (en) * | 2012-08-02 | 2012-12-05 | 清华大学 | Method for preparing graphene quantum dots |
| CN103325579A (en) * | 2013-06-20 | 2013-09-25 | 中南大学 | Reduction carbon quantum dot/RuO2 composite material and preparing and application method thereof |
| CN103626161A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN103738942A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene nano-rod preparation method |
| CN103738941A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene quantum dot preparation method |
| CN103845361A (en) * | 2014-03-19 | 2014-06-11 | 国家纳米科学中心 | Application of graphene quantum dot in preparing tumor therapy sensitizing agent |
| CN103965867A (en) * | 2014-04-09 | 2014-08-06 | 上海大学 | Preparation method for graphene quantum dot wrapping zinc oxide core-shell structure quantum dot for QD-LED |
-
2015
- 2015-05-22 CN CN201510268945.6A patent/CN104909356A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| CN102633257A (en) * | 2012-05-04 | 2012-08-15 | 东南大学 | Method for synthesizing less than 10 nm of single-layer graphene quantum dot biological imaging agent |
| CN102807209A (en) * | 2012-08-02 | 2012-12-05 | 清华大学 | Method for preparing graphene quantum dots |
| CN103626161A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN103325579A (en) * | 2013-06-20 | 2013-09-25 | 中南大学 | Reduction carbon quantum dot/RuO2 composite material and preparing and application method thereof |
| CN103738942A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene nano-rod preparation method |
| CN103738941A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene quantum dot preparation method |
| CN103845361A (en) * | 2014-03-19 | 2014-06-11 | 国家纳米科学中心 | Application of graphene quantum dot in preparing tumor therapy sensitizing agent |
| CN103965867A (en) * | 2014-04-09 | 2014-08-06 | 上海大学 | Preparation method for graphene quantum dot wrapping zinc oxide core-shell structure quantum dot for QD-LED |
Non-Patent Citations (2)
| Title |
|---|
| DENGYU PAN ETC.: "Hydrothermal Route for Cutting Graphene Sheets into Blue-Luminescent Graphene Quantum Dots", 《ADVANCED MATERIALS》 * |
| YU CHONG ETC.: "The in vitro and in vivo toxicity of graphene quantum dots", 《BIOMATERIALS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348281A (en) * | 2015-07-13 | 2017-01-25 | 南京理工大学 | Method for preparing bifluorescence graphene quantum dots hydrothermally |
| CN106219528A (en) * | 2016-07-26 | 2016-12-14 | 湖南师范大学 | A kind of controlled method preparing graphene oxide and graphene oxide quantum dot |
| CN106219528B (en) * | 2016-07-26 | 2018-06-15 | 湖南师范大学 | A kind of method of controllable preparation graphene oxide and graphene oxide quantum dot |
| CN107043104A (en) * | 2017-05-11 | 2017-08-15 | 桂林理工大学 | A kind of graphene quantum dot induces high nitrogen doped photo-reduction graphene oxide preparation method |
| CN107601466A (en) * | 2017-10-12 | 2018-01-19 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN107601466B (en) * | 2017-10-12 | 2018-08-03 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN110204991A (en) * | 2019-04-28 | 2019-09-06 | 西南石油大学 | A kind of efficient corrosion resisting h-BN/GO/ water-base epoxy composite material, preparation method and application |
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Application publication date: 20150916 |