CN104961125A - Graphene high in solubility and preparation method thereof - Google Patents
Graphene high in solubility and preparation method thereof Download PDFInfo
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- CN104961125A CN104961125A CN201510352445.0A CN201510352445A CN104961125A CN 104961125 A CN104961125 A CN 104961125A CN 201510352445 A CN201510352445 A CN 201510352445A CN 104961125 A CN104961125 A CN 104961125A
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Abstract
The invention discloses a preparation method of graphene high in solubility. The preparation method includes the steps that a, graphite oxide is prepared through a Hummers method; b, a chemical reducing agent is added to obtain reduced graphene oxide through hydrothermal reaction; c, ultrasonic treatment is performed on the reduced graphene oxide under ultrasonic conditions, and then microwave treatment is performed on the reduced graphene oxide for 5 mintues-30 minutes at the temperature of 80 DEG C-180 DEG C after the reduced graphene oxide is placed under microwave conditions. The graphene product prepared through the method is high in solubility, and the size of the product ranges from 20 nm to 500 nm. The purpose is to solve the technical problems that in the prior art, reduced graphene oxide is prone to clustering in a water solution and poor in solubility; the method is provided for solving the graphene on a large scale and applying the graphene widely, and the application range of the graphene is greatly enlarged.
Description
Technical field
The invention belongs to graphene new material technical field, relate to a kind of preparation method with the Graphene of high resolution.
Technical background
As the Two-dimensional Carbon material only with a carbon atomic layer, Graphene is just subject to the extensive concern of common people once emerging.The structure of its uniqueness and electron motion mode, excellent mechanical property, outstanding electromagnetic property, makes Graphene be with a wide range of applications in all many-sides.But in the production application of reality, Graphene is faced with many problems.Except the problem in manufacture, the main difficulty of restriction Graphene large-scale application is, Graphene is not soluble in water, ethanol and most organic solvent.
Due to the electronic structure of itself, graphenic surface enlivens a large amount of unbound electrons.The existence of these unbound electrons makes very easily electrostatic interaction to occur between adjacent Graphene, the weak interaction between π-π interaction equimolecular.These weak interactions make easily to be combined with each other between Graphene synusia.On the other hand, because the two-dirnentional structure thermodynamics of Graphene itself is also unstable, its surface has a large amount of gauffers and structure rises and falls.The existence of these folds and fluctuating makes graphenic surface easily occur electric field polarization, thus exacerbates the reunion of Graphene.
As the simple substance be made up of carbon, Graphene, at water, does not have good solubility in ethanol polar solvent.Meanwhile, due to the particular electrical minor structure on its surface, it is also not easy to dissolve in common most organic solvents such as DMF.Due to the characteristic of its not easily molten and easy reunion, make Graphene be difficult to storage and transport, in application process, also cannot ensure its homogeneity used simultaneously, thus have influence on the performance of product.Therefore, explore a kind of suitable aftertreatment technology, make Graphene in common solvent, have good solvability, not easily reunite simultaneously, become the large difficult point needing breakthrough in the application of current Graphene badly.
The Main Means solved the problem at present carries out modification to Graphene.Namely use other groups to modify to graphenic surface, thus reach the object making Graphene be easy to dissolving in certain solvent.But this method had both destroyed the structure of Graphene, on Graphene, introduce new group again, thus greatly have impact on the physicochemical property of Graphene itself.
Summary of the invention
The object of the invention is to solve in prior art, the Graphene dispersion of stable and uniform and the technological difficulties of dissolving in a solvent cannot be made, thus ground-breakingly provide a kind of high resolution that has, can the preparation method of grapheme material of dispersion of stable and uniform in water solvent.This preparation method under the prerequisite of various physicochemical properties not destroying Graphene, can strengthen the solvability of Graphene greatly.
Through long-term research, contriver finds that grapheme material is not soluble and the major cause that is easy to reunite has a large amount of molecular interactions between its inner Graphene synusia.Thus, contriver uses extraneous energy to impact graphene dispersion system, its molecular interaction is weakened even destroyed, thus reaches the deliquescent effect improving grapheme material.In order to not destroy the electronic structure of Graphene itself, contriver uses the method for microwave exposure to process grapheme material.By the time and temperature that control reaction, grapheme material Middle molecule intermolecular forces is impacted.Through experimental results demonstrate, in microwave instrument, irradiation is carried out to the dispersion liquid of Graphene.Temperature is at 80-180 DEG C, and the time, at 5-30 minute, can not be affected Graphene physical and chemical performance, has the grapheme material of high resolution simultaneously.
The present invention is the control by temperature and time, on the basis of redox graphene, carries out microwave exposure to it, thus destroys its Intermolecular Forces, obtain the grapheme material with high resolution.
Therefore, the invention provides a kind of preparation method with the Graphene of high resolution, there is following process and step:
A, by Hummers legal system for graphite oxide, specific practice is under the condition of ice bath cooling and stirring, toward dense H
2sO
4in add NaNO
3, then graphite is added wherein while stirring, then slowly add KMnO
4, to ensure that temperature is lower than 20 DEG C, removes ice bath, use water-bath and maintain the temperature at 35 DEG C, being incubated 2 hours, under then stirring, slowly adding deionized water, system is fiercely warmed up to 98 DEG C, keeps 15 minutes, then dilute further with deionized water with 98 DEG C of water-baths, finally add remaining potassium permanganate and Manganse Dioxide in 30% hydrogen peroxide reduction system, obtain glassy yellow system, filtered while hot, wash with hydrochloric acid soln, washing, drying obtains graphite oxide;
B, graphite oxide is put into hydrothermal reaction kettle, add deionized water wiring solution-forming, then naturally cool to room temperature after adding chemical reducing agent hydro-thermal reaction, suction filtration, dry and obtain redox graphene;
C, freshly prepared redox graphene is ultrasonic under Ultrasonic Conditions, then put in 80-180 DEG C of microwave treatment 5-30 minute under microwave condition, after leaving standstill after gained takes out product.
Further, chemical reducing agent in stepb can be hydrazine hydrate, add hydrazine hydrate and the graphite oxide aqueous solution volume ratio be 1:40.
Further, chemical reducing agent in stepb can be sodium borohydride, and the ratio of the sodium borohydride added is add 1mg in every 4mL graphite oxide aqueous solution.
Further, hydrothermal reaction condition is in stepb 120 DEG C of insulation 4h.
Further, bake out temperature in stepb controls at 45 DEG C.
Finally obtain product size size at 20-500nm.
The present invention compared with prior art has following useful effect:
Grapheme material prepared by the present invention has the feature of the high resolution not available for general Graphene, and technique is simple, with low cost.In the process addressed this problem, do not destroy the structure of matter and the electronic configuration of Graphene itself simultaneously.Thus drop to minimum on the impact of the physical and chemical performance of Graphene itself.The Graphene utilizing the method to prepare can be uniformly distributed in water solvent, and can preserve for a long time and transport, thus greatly facilitates the use of Graphene, has expanded its use range.
Accompanying drawing explanation
Fig. 1: high resolution Graphene sample Raman schemes
Fig. 2: redox graphene sample Raman schemes
Fig. 3: high resolution Graphene sample TEM schemes
Fig. 4: redox graphene sample TEM schemes.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
Under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Slowly add 9g KMnO
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system and Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.Prepared graphite oxide (GO) is put into hydrothermal reaction kettle, adds deionized water to 40ml, add chemical reducing agent hydrazine hydrate 1ml, hydro-thermal reaction 120 DEG C insulation 4h, naturally cools to room temperature.Gained system 0.22um aperture millipore filtration suction filtration.Products therefrom 45 DEG C oven dry is redox graphene.Prepared Graphene is put into microwave instrument, in 80 DEG C of insulations 30 minutes.Leaving standstill after products obtained therefrom takes out 7 days is sample 1.
Embodiment 2:
Under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Slowly add 9g KMnO
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system and Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.Prepared graphite oxide (GO) is put into hydrothermal reaction kettle, adds deionized water to 40ml, add chemical reducing agent 10mg sodium borohydride, hydro-thermal reaction 120 DEG C insulation 4h, naturally cools to room temperature.Gained system 0.22um aperture millipore filtration suction filtration.Products therefrom 45 DEG C oven dry is redox graphene.Prepared Graphene is put into microwave instrument, in 140 DEG C of insulations 10 minutes.Leaving standstill after products obtained therefrom takes out 7 days is sample 2.
Embodiment 3:
Under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Slowly add 9g KMnO
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system and Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.Prepared graphite oxide (GO) is put into hydrothermal reaction kettle, adds deionized water to 40ml, add chemical reducing agent hydrazine hydrate 1ml, hydro-thermal reaction 120 DEG C insulation 4h, naturally cools to room temperature.Gained system 0.22um aperture millipore filtration suction filtration.Products therefrom 45 DEG C oven dry is redox graphene.Prepared Graphene is put into microwave instrument, and 180 DEG C are incubated 5 minutes.Leaving standstill after products obtained therefrom takes out 7 days is sample 3.
Comparative example (without microwave treatment):
Under the condition that ice bath cools and stirs, toward the dense H of 69ml
2sO
4in add 1.5gNaNO
3(grinding), waits NaNO
3be dissolved in H completely
2sO
4in after, by 3g graphite limit stir just add wherein.Slowly add 9g KMnO
4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 hours.Stir lower slowly (starting very slow) and add 137ml deionized water, system is fiercely warmed up to 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420ml is diluted to further with warm (60 DEG C) deionized water, then add 30% hydrogen peroxide 11ml(refer to excessive) with potassium permanganate remaining in reduction system and Manganse Dioxide, obtain glassy yellow system.Filtered while hot, then washs once with the hydrochloric acid soln that volume ratio is 1:10, washes three times.45 DEG C of dryings in an oven.Prepared graphite oxide (GO) is put into hydrothermal reaction kettle, adds deionized water to 40ml, add chemical reducing agent 10mg sodium borohydride, hydro-thermal reaction 120 DEG C insulation 4h, naturally cools to room temperature.Gained system 0.22um aperture millipore filtration suction filtration.Products therefrom 45 DEG C oven dry is redox graphene.Leaving standstill after taking out 7 days is sample 4.
Graphene through method process provided by the present invention has good solubility, dissolution homogeneity.And in redox graphene dispersion liquid without method process provided by the present invention, there is obvious layering in Graphene and water.By Fig. 1 and Fig. 2, and the contrast of Fig. 3 and Fig. 4, in structure and pattern, there is not notable difference with raw sample in the Graphene sample through present method process.Illustrate that structure and the physicochemical property of Graphene do not receive obvious impact.
Claims (5)
1. there is a preparation method for the Graphene of high resolution, it is characterized in that there is following process and step:
A, by Hummers legal system for graphite oxide, specific practice is under the condition of ice bath cooling and stirring, toward dense H
2sO
4in add NaNO
3, then graphite is added wherein while stirring, then slowly add KMnO
4, to ensure that temperature is lower than 20 DEG C, removes ice bath, use water-bath and maintain the temperature at 35 DEG C, being incubated 2 hours, under then stirring, slowly adding deionized water, system is fiercely warmed up to 98 DEG C, keeps 15 minutes, then dilute further with deionized water with 98 DEG C of water-baths, finally add remaining potassium permanganate and Manganse Dioxide in 30% hydrogen peroxide reduction system, obtain glassy yellow system, filtered while hot, wash with hydrochloric acid soln, washing, drying obtains graphite oxide;
B, graphite oxide is put into hydrothermal reaction kettle, add deionized water wiring solution-forming, then naturally cool to room temperature after adding chemical reducing agent hydro-thermal reaction, suction filtration, dry and obtain redox graphene;
C, freshly prepared redox graphene is ultrasonic under Ultrasonic Conditions, then put in 80-180 DEG C of microwave treatment 5-30 minute under microwave condition, after leaving standstill after gained takes out product.
2. a kind of preparation method with the Graphene of high resolution as claimed in claim 1, is characterized in that the chemical reducing agent in step b can be hydrazine hydrate, add hydrazine hydrate and the graphite oxide aqueous solution volume ratio be 1:40.
3. a kind of preparation method with the Graphene of high resolution as claimed in claim 1, it is characterized in that the chemical reducing agent in step b can be sodium borohydride, the ratio of the sodium borohydride added is add 1mg in every 4mL graphite oxide aqueous solution.
4. a kind of preparation method with the Graphene of high resolution as claimed in claim 1, is characterized in that the hydrothermal reaction condition in step b is 120 DEG C of insulation 4h.
5. a kind of preparation method with the Graphene of high resolution as claimed in claim 1, is characterized in that the bake out temperature in step b controls at 45 DEG C.
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Cited By (8)
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| CN105838187A (en) * | 2016-04-23 | 2016-08-10 | 上海大学 | Ball milling preparation method and application of graphene oxide anticorrosive coating |
| CN106115796A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Preparation method of graphene-manganese dioxide nano material containing magnetic iron |
| CN106865529A (en) * | 2017-03-30 | 2017-06-20 | 南开大学 | A kind of preparation method of the microwave radiation technology high-quality redox graphene of triggering mode |
| CN107500275A (en) * | 2017-10-20 | 2017-12-22 | 山东重山光电材料股份有限公司 | A kind of method for producing different Oil repellent fluorinated graphenes in enormous quantities |
| CN107539984A (en) * | 2017-10-19 | 2018-01-05 | 苏州方卓材料科技有限公司 | The preparation method of graphite material |
| CN108201531A (en) * | 2016-12-19 | 2018-06-26 | 湖南尔康湘药制药有限公司 | Segmented intestine targeted starch capsule of highly dissoluble sulbenicillin sodium and preparation method thereof |
| CN108390064A (en) * | 2018-01-19 | 2018-08-10 | 同济大学 | A kind of graphene-based flexible self-supporting mixed gel electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838187A (en) * | 2016-04-23 | 2016-08-10 | 上海大学 | Ball milling preparation method and application of graphene oxide anticorrosive coating |
| CN106115796A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Preparation method of graphene-manganese dioxide nano material containing magnetic iron |
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| CN108201531A (en) * | 2016-12-19 | 2018-06-26 | 湖南尔康湘药制药有限公司 | Segmented intestine targeted starch capsule of highly dissoluble sulbenicillin sodium and preparation method thereof |
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| CN109872831A (en) * | 2017-12-04 | 2019-06-11 | 北京市合众创能光电技术有限公司 | Compound silver paste of modified graphene and preparation method thereof |
| CN108390064A (en) * | 2018-01-19 | 2018-08-10 | 同济大学 | A kind of graphene-based flexible self-supporting mixed gel electrode and preparation method thereof |
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Application publication date: 20151007 |