CN105565305A - Method for preparing graphene by using green reducing agent - Google Patents
Method for preparing graphene by using green reducing agent Download PDFInfo
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- CN105565305A CN105565305A CN201511005639.XA CN201511005639A CN105565305A CN 105565305 A CN105565305 A CN 105565305A CN 201511005639 A CN201511005639 A CN 201511005639A CN 105565305 A CN105565305 A CN 105565305A
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Abstract
The invention discloses a method for preparing graphene by using a green reducing agent, and relates to the technical field of graphene. The method comprises the steps: firstly, preparing graphite oxide by using a Hurmers method, and then stripping by ultrasonic waves to form a graphene oxide solution; then under an alkaline condition, reducing graphene oxide by using L-tyrosine as a reducing agent to obtain reduced graphene; and finally, washing with water, centrifuging and carrying out freeze vacuum drying to obtain a graphene powder. The green environmental-protection reducing agent is used for preparation of graphene. Compared with a traditional reducing agent, the used reducing agent has the advantages of low cost, no toxicity, and green and environmental protection; the prepared graphene has the advantages of larger specific surface area, high-temperature resistance, corrosion resistance, high strength, and good electrical conductivity, can be applied in the fields of smart clothing, lithium ion batteries, super capacitors, anti-corrosion coatings, military aerospace materials and the like.
Description
Technical field:
The present invention relates to technical field of graphene, be specifically related to a kind of method utilizing green reducing agent to prepare Graphene.
Background technology:
Graphene is that a kind of special each carbon atom is with SP
2the carbonaceous material of the individual layer bi-dimensional cellular shape structure of the tightly packed one-tenth of form of hydridization, cause has high-specific surface area, surface has the hydrophilic and excellent properties such as hydrophobicity, outstanding heat conductivility and mechanical property, outstanding electron transmission performance, and recent years all causes great concern in fields such as water treatment, high performance energy memory device, sensor, matrix material, sterilizations.
The method preparing Graphene at present has: mechanically peel method, epitaxial growth method, chemical vapor infiltration and graphite oxide reduction method etc.It is relatively simple that mechanically peel method has operating process, and quality product is high, and be the main method preparing individual layer, high-quality Graphene, but the dimensional controllability of product is poor, efficiency is low, and cost is high, and is not suitable for scale operation.Epitaxial growth method comprises silicon carbide epitaxial growth method and metal catalytic epitaxial growth method.Epitaxial growth method refers at high temperature under condition, at certain substrate surface deposited graphite alkene.Prepared Graphene mostly is individual layer, and can prepare uniform Graphene in large area.But the cost of product is high, yields poorly and be not suitable for scale operation.CVD can prepare high quality, large-area graphene film.Oxidation reduction process can be mass-produced graphene powder.The method is simple to operate, preparation cost is low, can large-scale industrial production, has become effective way prepared by Graphene.
At present, the reductive agent that chemical method prepares Graphene has hydrazine hydrate, sodium borohydride, HI acid etc.Wherein, hydrazine hydrate and HI acid toxic, the inflammable and explosive property of sodium borohydride, causes there is certain danger in extensive reduction production process.Secondly, the price of HI acid is high, adds production cost, constrains suitability for industrialized production.
TYR is a kind of green, nontoxic amino acid, has certain reductibility in the basic conditions.Utilize TYR to prepare redox graphene (rGO), its reductive condition is simple, the method process is easy to operate, green non-poisonous, be convenient to suitability for industrialized production, thus can produce the cost of low Graphene.
Summary of the invention:
Technical problem to be solved by this invention be to provide a kind of simple to operate, processing step is few, cost is low, the green reducing agent that utilizes of environment-protecting asepsis prepares the method for Graphene.
Technical problem to be solved by this invention adopts following technical scheme to realize:
Utilize green reducing agent to prepare the method for Graphene, comprise the steps:
(1) preparation of graphite oxide: in ice-water bath, in the vitriol oil, Graphite Powder 99, SODIUMNITRATE and potassium permanganate is added successively under stirring, controlling temperature of reaction is 0 ~ 20 DEG C, 35 DEG C are warmed up to after reaction 0 ~ 60min, continue to stir 30min, slowly add deionized water, then be heated to 70 ~ 90 DEG C continue to stir 30min, adding hydrogen peroxide again makes solution become glassy yellow, filtered while hot, and with 5%HCl solution and deionized water wash until in filtrate sulfate radical-free be detected, finally that filter cake is fully dry, save backup;
(2) preparation of graphene oxide: add deionized water in graphite oxide prepared by step (1), be then placed in Ultrasonic Cleaners ultrasonic, obtain graphene oxide;
(3) reduction of graphene oxide: get graphene oxide solution prepared by step (2), alkali lye regulator solution pH value is added under stirring, then green reducing agent is added in the basic conditions, stirring reaction after heating up, reaction terminates rear centrifugal, product is after washed several times with water, and lyophilize obtains Graphene.
In described step (1), ice-water bath temperature is 0 ~ 5 DEG C, the mass ratio of Graphite Powder 99, SODIUMNITRATE and potassium permanganate is 2:1:6, the solid-to-liquid ratio of Graphite Powder 99 and the vitriol oil is 3g:23mL ~ 1g:23mL, and the solid-to-liquid ratio of Graphite Powder 99 and deionized water is 3g:110mL ~ 1g:110mL.
In described step (2), ultrasonic power is 0 ~ 150W, and graphite oxide concentration is 0 ~ 1mg/mL, and Ultrasonic Cleaners water temperature is no more than 10 DEG C.
To be that ammoniacal liquor, potassium hydroxide or sodium hydroxide add water formulated for alkali lye in described step (3), and regulator solution pH is 9 ~ 12.
In described step (3), temperature of reaction is 35 ~ 95 DEG C, and the reaction times is 2 ~ 48h.
Described step (3) Green reductive agent is TYR.
The mass ratio of described graphene oxide and TYR is 1:1 ~ 10:1.
The invention has the beneficial effects as follows:
(1) the present invention adopts the reductive agent of environmental protection to prepare Graphene, and compared with traditional reductive agent, the present invention's reductive agent used cost is low, nontoxic, environmental protection;
(2) preparation process step of the present invention is few, and technique is simple, it is simple and easy to operate, and is convenient to suitability for industrialized production;
(3) the present invention adopts TYR as reductive agent, prepared Graphene possesses larger specific surface area, high temperature resistant, corrosion-resistant, high strength, good conductivity, can be applicable to the fields such as intelligence wearing, lithium ion battery, ultracapacitor, protective system, militay space flight material.
Accompanying drawing illustrates:
Fig. 1 is that the Graphene UV-Vis that the present invention is prepared the different recovery time schemes;
Fig. 2 is that graphene oxide AFM prepared by the present invention schemes;
Fig. 3 is the recovery time of the present invention is that Graphene AFM prepared by 2h schemes;
Fig. 4 is the recovery time of the present invention is that Graphene AFM prepared by 24h schemes;
Fig. 5 is the recovery time of the present invention is that Graphene TEM prepared by 8h schemes
Fig. 6 is that the graphene oxide prepared of the present invention and Graphene Raman scheme;
Fig. 7 is that the Graphene Raman that the present invention is prepared the different recovery time schemes.
Embodiment:
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
(1) graphene oxide preparation; Temperature of reaction is 0 ~ 5 DEG C, in the 23mL vitriol oil, adds 1g Graphite Powder 99,0.5g SODIUMNITRATE and 3g potassium permanganate successively, mixing solutions magnetic agitation 0 ~ 60min; Be warmed up to 35 DEG C, continue to stir 30min, slowly add 110mL deionized water; Be heated to 90 DEG C, keep stirring 30min, then add 18mL hydrogen peroxide, filtered while hot; And with 5%HCl solution and deionized water wash until in filtrate sulfate radical-free be detected, finally by filtration cakes torrefaction;
(2), under the graphene oxide solution of dose volume 100mL, massfraction 0.2%, magnetic agitation condition, NH is dripped
3h
2o adjust ph about about 10;
(3) take quality 0.02gL-tyrosine, join in 100mL volumetric flask, be mixed with the TYR solution that concentration is 0.2mg/mL;
(4) the TYR solution of preparation is joined in the mixing solutions of step (2), under 95 DEG C of water bath condition, magnetic agitation 8h.Centrifugal, filter cake washed several times with water, dries.
Embodiment 2
(1) with embodiment 1;
(2) graphene oxide solution of dose volume 100mL, massfraction 0.1%, under magnetic agitation condition, drips NH
3h
2o adjust ph about about 10;
(3) take quality 0.01gL-tyrosine, join in 100mL volumetric flask, be mixed with the TYR solution that concentration is 0.1mg/mL;
(4) the TYR solution of preparation is joined in the mixing solutions of step (2), under 95 DEG C of water bath condition, magnetic agitation 8h.Centrifugal, washed several times with water, dries.
Embodiment 3
(1) with embodiment 1;
(2) graphene oxide solution of dose volume 100mL, massfraction 0.05%, under magnetic agitation condition, drips NH
3h
2o adjust ph about about 10;
(3) take the TYR of quality 0.01g, join in 100mL volumetric flask, be mixed with the TYR solution that concentration is 0.1mg/mL;
(4) the TYR solution of preparation is joined in the mixing solutions of step (2), under 95 DEG C of water bath condition, magnetic agitation 8h.Centrifugal, washed several times with water, dries.
Embodiment 4
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) join in the mixing solutions of step (2) by the TYR solution of preparation, under 95 DEG C of water bath condition, magnetic agitation 2h, 4h, 6h, then get 100mL reaction soln respectively, centrifugal, washed several times with water, dries.
Embodiment 5
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) join in the mixing solutions of step (2) by the TYR solution of preparation, under 35 DEG C of water bath condition, during magnetic agitation 8h, then centrifugal, washed several times with water, dries.
Embodiment 6
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) join in the mixing solutions of step (2) by the TYR solution of preparation, under 65 DEG C of water bath condition, magnetic agitation 8h, then centrifugal, washed several times with water, dries.
Embodiment 7
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) join in the mixing solutions of step (2) by the TYR solution of preparation, under 95 DEG C of oil bath conditions, magnetic agitation 24h, then centrifugal, washed several times with water, dries.
In embodiment 7, the conductivity of prepared redox graphene is better, and specific conductivity can reach about 138S/m, and its pattern as shown in Figure 4.
The present invention pays attention to L-TYR and makees reductive agent and prepare Graphene, to its downstream application, as ultracapacitor, lithium electricity, solar cell, impregnating material etc., any apply on basis of the present invention all in protection scope of the present invention.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. utilize green reducing agent to prepare the method for Graphene, it is characterized in that, comprise the steps:
(1) preparation of graphite oxide: in ice-water bath, in the vitriol oil, Graphite Powder 99, SODIUMNITRATE and potassium permanganate is added successively under stirring, controlling temperature of reaction is 0 ~ 20 DEG C, 35 DEG C are warmed up to after reaction 0 ~ 60min, continue to stir 30min, slowly add deionized water, then be heated to 70 ~ 90 DEG C continue to stir 30min, adding hydrogen peroxide again makes solution become glassy yellow, filtered while hot, and with 5%HCl solution and deionized water wash until in filtrate sulfate radical-free be detected, finally that filter cake is fully dry, save backup;
(2) preparation of graphene oxide: add deionized water in graphite oxide prepared by step (1), be then placed in Ultrasonic Cleaners ultrasonic, obtain graphene oxide;
(3) reduction of graphene oxide: get graphene oxide solution prepared by step (2), alkali lye regulator solution pH value is added under stirring, then green reducing agent is added in the basic conditions, stirring reaction after heating up, reaction terminates rear centrifugal, product is after washed several times with water, and lyophilize obtains Graphene.
2. the method utilizing green reducing agent to prepare Graphene according to claim 1, it is characterized in that: in described step (1), ice-water bath temperature is 0 ~ 5 DEG C, the mass ratio of Graphite Powder 99, SODIUMNITRATE and potassium permanganate is 2:1:6, the solid-to-liquid ratio of Graphite Powder 99 and the vitriol oil is 3g:23mL ~ 1g:23mL, and the solid-to-liquid ratio of Graphite Powder 99 and deionized water is 3g:110mL ~ 1g:110mL.
3. the method utilizing green reducing agent to prepare Graphene according to claim 1, is characterized in that: in described step (2), ultrasonic power is 0 ~ 150W, and graphite oxide concentration is 0 ~ 1mg/mL, and Ultrasonic Cleaners water temperature is no more than 10 DEG C.
4. the method utilizing green reducing agent to prepare Graphene according to claim 1, is characterized in that: to be that ammoniacal liquor, potassium hydroxide or sodium hydroxide add water formulated for alkali lye in described step (3), and regulator solution pH is 9 ~ 12.
5. the method utilizing green reducing agent to prepare Graphene according to claim 1, is characterized in that: in described step (3), temperature of reaction is 35 ~ 95 DEG C, and the reaction times is 2 ~ 48h.
6. the method utilizing green reducing agent to prepare Graphene according to claim 1, is characterized in that: described step (3) Green reductive agent is TYR.
7. the method utilizing green reducing agent to prepare Graphene according to claim 6, is characterized in that: the mass ratio of described graphene oxide and TYR is 1:1 ~ 10:1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587035A (en) * | 2016-11-23 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Eco-friendly safe reducing agent-based graphene and its preparation and application |
| CN106853965A (en) * | 2016-12-30 | 2017-06-16 | 绍兴文理学院 | A kind of preparation method of negative material Graphene and electrochemical property test method |
| CN106938845A (en) * | 2017-03-10 | 2017-07-11 | 华南理工大学 | A kind of graphite oxide positive electrode and preparation method for lithium ion battery, the preparation method of lithium ion cell positive |
| CN108046242A (en) * | 2017-12-20 | 2018-05-18 | 昆明理工大学 | A kind of preparation method of poroid graphene |
| CN108193209A (en) * | 2017-12-30 | 2018-06-22 | 苏州市汉宜化学有限公司 | A kind of water base plating silver protecting agent of high stability and preparation method thereof |
| CN108584926A (en) * | 2018-05-23 | 2018-09-28 | 大同新成新材料股份有限公司 | A kind of micro crystal graphite prepares graphene method |
| CN109322146A (en) * | 2018-09-29 | 2019-02-12 | 南通大学 | The environment-friendly type carrying method of graphene on a kind of wool fiber |
| CN111875991A (en) * | 2020-08-11 | 2020-11-03 | 湖南大学 | Preparation method of poly (2-aminothiazole) modified graphene and epoxy composite coating |
-
2015
- 2015-12-28 CN CN201511005639.XA patent/CN105565305A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587035A (en) * | 2016-11-23 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Eco-friendly safe reducing agent-based graphene and its preparation and application |
| CN106853965A (en) * | 2016-12-30 | 2017-06-16 | 绍兴文理学院 | A kind of preparation method of negative material Graphene and electrochemical property test method |
| CN106938845A (en) * | 2017-03-10 | 2017-07-11 | 华南理工大学 | A kind of graphite oxide positive electrode and preparation method for lithium ion battery, the preparation method of lithium ion cell positive |
| CN108046242A (en) * | 2017-12-20 | 2018-05-18 | 昆明理工大学 | A kind of preparation method of poroid graphene |
| CN108193209A (en) * | 2017-12-30 | 2018-06-22 | 苏州市汉宜化学有限公司 | A kind of water base plating silver protecting agent of high stability and preparation method thereof |
| CN108584926A (en) * | 2018-05-23 | 2018-09-28 | 大同新成新材料股份有限公司 | A kind of micro crystal graphite prepares graphene method |
| CN109322146A (en) * | 2018-09-29 | 2019-02-12 | 南通大学 | The environment-friendly type carrying method of graphene on a kind of wool fiber |
| CN111875991A (en) * | 2020-08-11 | 2020-11-03 | 湖南大学 | Preparation method of poly (2-aminothiazole) modified graphene and epoxy composite coating |
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