CN104961125A - Graphene high in solubility and preparation method thereof - Google Patents

Graphene high in solubility and preparation method thereof Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
graphene
add
resolution
graphite oxide
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510352445.0A
Other languages
Chinese (zh)
Inventor
周忠福
俞健舒
李建伟
王会利
王清露
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN201510352445.0A priority Critical patent/CN104961125A/en
Publication of CN104961125A publication Critical patent/CN104961125A/en
Pending legal-status Critical Current

Links

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

A kind of Graphene with high resolution and preparation method thereof
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.
CN201510352445.0A 2015-06-24 2015-06-24 Graphene high in solubility and preparation method thereof Pending CN104961125A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510352445.0A CN104961125A (en) 2015-06-24 2015-06-24 Graphene high in solubility and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510352445.0A CN104961125A (en) 2015-06-24 2015-06-24 Graphene high in solubility and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104961125A true CN104961125A (en) 2015-10-07

Family

ID=54215258

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510352445.0A Pending CN104961125A (en) 2015-06-24 2015-06-24 Graphene high in solubility and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104961125A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
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 A kind of preparation method containing ferromagnetic Graphene nano material of manganese dioxide
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830459A (en) * 2010-05-20 2010-09-15 复旦大学 Method for preparing dry graphene powder
CN102275903A (en) * 2011-05-24 2011-12-14 东华大学 Preparation method of graphene and manganese dioxide composite material
CN102746123A (en) * 2012-06-30 2012-10-24 浙江工业大学 Method of preparing dibenzyl ether from benzyl alcohol under catalysis of graphene oxide
CN103787316A (en) * 2013-12-31 2014-05-14 深圳粤网节能技术服务有限公司 Oxidized graphene based on mixed acid system and preparation method of graphene
CN104692374A (en) * 2015-03-17 2015-06-10 济宁利特纳米技术有限责任公司 Preparation method of high-concentration graphene dispersion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830459A (en) * 2010-05-20 2010-09-15 复旦大学 Method for preparing dry graphene powder
CN102275903A (en) * 2011-05-24 2011-12-14 东华大学 Preparation method of graphene and manganese dioxide composite material
CN102746123A (en) * 2012-06-30 2012-10-24 浙江工业大学 Method of preparing dibenzyl ether from benzyl alcohol under catalysis of graphene oxide
CN103787316A (en) * 2013-12-31 2014-05-14 深圳粤网节能技术服务有限公司 Oxidized graphene based on mixed acid system and preparation method of graphene
CN104692374A (en) * 2015-03-17 2015-06-10 济宁利特纳米技术有限责任公司 Preparation method of high-concentration graphene dispersion

Cited By (8)

* Cited by examiner, † Cited by third party
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 A kind of preparation method containing ferromagnetic Graphene nano material of manganese dioxide
CN106115796B (en) * 2016-06-29 2017-12-08 广西桂柳化工有限责任公司 A kind of preparation method of the graphene nano material of manganese dioxide containing Armco magnetic iron
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
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
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
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
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

Similar Documents

Publication Publication Date Title
Zhai et al. Phosphate ion functionalized Co3O4 ultrathin nanosheets with greatly improved surface reactivity for high performance pseudocapacitors
Hwang et al. Poly (vinyl alcohol) reinforced and toughened with poly (dopamine)-treated graphene oxide, and its use for humidity sensing
Lu et al. Elastic, conductive, polymeric hydrogels and sponges
JP6640881B2 (en) Super-flexible highly thermally conductive graphene film and method for producing the same
Liu et al. One‐step synthesis of single‐layer MnO2 nanosheets with multi‐role sodium dodecyl sulfate for high‐performance pseudocapacitors
Wang et al. Fe3O4 nanoparticles grown on graphene as advanced electrode materials for supercapacitors
Luo et al. Self-standing polypyrrole/black phosphorus laminated film: promising electrode for flexible supercapacitor with enhanced capacitance and cycling stability
CN103537236B (en) A kind of preparation method of graphene aerogel
Li et al. Functional gels based on chemically modified graphenes
CN102941042B (en) A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof
Tang et al. Facile synthesis of 3D reduced graphene oxide and its polyaniline composite for super capacitor application
WO2017084561A1 (en) Preparation method for large-size graphene oxide or graphene
Li et al. A highly porous polyaniline-graphene composite used for electrochemical supercapacitors
CN104250005B (en) A kind of graphene aerogel and its preparation method and application
CN105271217B (en) A kind of preparation method of the three-dimensional grapheme of N doping
Feng et al. A low-temperature method to produce highly reduced graphene oxide
Jung et al. A facile route for 3D aerogels from nanostructured 1D and 2D materials
Valentini et al. A novel method to prepare conductive nanocrystalline cellulose/graphene oxide composite films
Paredes et al. Environmentally friendly approaches toward the mass production of processable graphene from graphite oxide
Whitby et al. Driving forces of conformational changes in single-layer graphene oxide
Yang et al. Preparation of poly (3-hexylthiophene)/graphene nanocomposite via in situ reduction of modified graphite oxide sheets
Liu et al. Aniline as a dispersing and stabilizing agent for reduced graphene oxide and its subsequent decoration with Ag nanoparticles for enzymeless hydrogen peroxide detection
CN102694171B (en) Hydrothermal preparation method for composite material of single-layer WS2 and graphene
Luo et al. Flexible carbon nanotube/polyurethane electrothermal films
Ouyang et al. Scalable preparation of three-dimensional porous structures of reduced graphene oxide/cellulose composites and their application in supercapacitors

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151007