CN104724697B - A kind of microwave-assisted prepares the method for graphene oxide - Google Patents
A kind of microwave-assisted prepares the method for graphene oxide Download PDFInfo
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- CN104724697B CN104724697B CN201410422552.1A CN201410422552A CN104724697B CN 104724697 B CN104724697 B CN 104724697B CN 201410422552 A CN201410422552 A CN 201410422552A CN 104724697 B CN104724697 B CN 104724697B
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Abstract
The invention discloses a kind of method that microwave-assisted prepares graphene oxide, mainly comprise the steps: 1) under strong acid environment, graphite is mixed with oxidant potassium permanganate；2) the low power microwave radiation auxiliary intercalation graphite oxide powder having no report is used to prepare graphite oxide；3) in deionized water ultrasonic for graphite oxide stripping is prepared graphene oxide colloidal sol.Graphene oxide yield is higher than 95%.Compared with prior art, preparation process of the present invention is simple, is greatly shortened preparation time particularly by microwave radiation auxiliary graphite intercalation oxidation, and material reaction is abundant, and productivity improves, and favorable reproducibility, can accomplish scale production.
Description
Technical field
The present invention relates to a kind of method that microblogging auxiliary prepares graphene oxide.
Background technology
Graphene has sp2nullSix side's conjugated structures of hydridization，It it is a kind of stable two dimensional crystal material，Owing to it is in electricity、Optics、The aspect such as calorifics and mechanics shows many excellent properties，Greatly excite the research enthusiasm of association area scientific research personnel，In recent years about this material at energy storage [M.Pumera.Graphene-based nanomaterials for energy storage [J] .Energy Environ.Sci.,2011,(4),668-674]、Liquid crystal device [P.Blake,P.D.Brimicombe,R.R.Nair,T.J.Booth.Graphene-Based Liquid Crystal Device[J].Nano Lett.,2008，8(6):1704-1708]、Electronic device (N.O.Weiss,H.Zhou,L.Liao,Y.Liu.Graphene:An Emerging Electronic Material[J].Adv.Mater.,2012,24 (43): 5782-825] and catalyst carrier [M.M.Liu,R.Z.Zhang,and W.Chen.Graphene-Supported Nanoelectrocatalysts for Fuel Cells:Synthesis,Properties,and Applications[J].Chem.Rev.,2014,114 (10): 5117-5160] etc. the applied research report in field increases sharply，Demonstrate the application prospect that this material is wide.
At present, the preparation method of Graphene has chemical vapour deposition technique, epitaxial growth method, mechanical stripping method and oxidation-reduction method.Owing to oxidation-reduction method preparation technology is simple, with low cost, can be mass, so having high researching value.
Graphene oxide is that the oxidation of lamellar graphite powder is peeled off products therefrom, owing to containing the oxy radical such as great amount of hydroxy group, carboxyl on its Two-dimensional Carbon skeleton and edge, uniform, stable Monolayer Dispersion system [D.R.Dreyer can be formed in water, A.D.Todd, C.W.Bielawski.Harnessing the chemistry of graphene oxide [J] .Chem.Soc.Rev., 2014,43:5288-5301].nullAnd these oxy radicals easily react with some chemical substances，Obtain modified graphene and graphene-based composite，Such as Feng Yan et al.，Zinc oxide-redox graphene composite [Y.Feng by solvent-thermal method fabricated in situ,N.N.Feng,Y.Z.Wei,G.Y.Zhang.An in situ gelatin-assisted hydrothermal synthesis of ZnO–reduced graphene oxide composites with enhanced photocatalytic performance under ultraviolet and visible light[J].RSC Adv.,2014,4:7933-7943].Exactly because graphene oxide has above-mentioned good physical compatibility performance and chemical bond performance so that it is not only can be prepared Graphene by direct-reduction batch, also provide more possibilities for synthetic graphite olefinic base material.
There is the multiple method preparing graphene oxide, such as at present: the patent of Publication No. CN103539108A is to prepare graphite oxide by two-step penetration method, then prepared by its stripping graphene oxide；Crystalline flake graphite oxidation is prepared graphite oxide for oxidant with potassium permanganate under mixed acid environment and heating condition by Daniela C. etc., then peeled off and prepared graphene oxide [D.C.Marcano, D.V.Kosynkin, J.M.Berlin.Improved Synthesis of Graphene Oxide [J] .ACS Nano
2010,4(8):4806-4814]；The positive light of Zou etc. then prepares graphene oxide [Zou Zhengguang by ultrasonic wave added Hummers method, Yu Huijiang, Long Fei, Fan Yanhuang. ultrasonic wave added Hummers method prepares graphene oxide [J]. Chinese Journal of Inorganic Chemistry, 2011,27 (9): 1753-1757], but these methods exist or operation complexity, the longest, or poor reproducibility, or degree of oxidation is uneven etc. not enough.Therefore, a kind of high efficiency of exploitation, high yield, good stability, operating process is manageable, and to prepare graphite oxide technology significant.
Summary of the invention
The present invention proposes a kind of method preparing graphene oxide for raw material with graphite powder; the method overcome that existing graphene oxide technology of preparing exists productivity is low, material reaction not exclusively, react the drawbacks such as uneven, time-consuming length; and preparation process favorable reproducibility, is suitable for low cost, the needs of large-scale production.
The present invention is achieved by the following technical programs:
(1) it is 800r min at rotating speed-1～2000r min-1Magnetic agitation under, graphite powder and strong oxidizer potassium permanganate are added in strong acid mix homogeneously respectively, wherein graphite powder can be crystalline graphite powder, natural graphite powder, expanded graphite powder or expansible graphite powder；Potassium permanganate consumption is 1g graphite powder potassium permanganate 3g～6g；Strong acid can be commercially available concentrated sulphuric acid, it is possible to for the mixed acid of commercially available concentrated sulphuric acid Yu strong phosphoric acid, V in mixed acidConcentrated sulphuric acid:VStrong phosphoric acidThe mass concentration of >=4:1, concentrated sulphuric acid and strong phosphoric acid is all not less than 92%, and the consumption of acid is 1g graphite powder acid 30ml～100ml；
(2) controlling stir speed (S.S.) is 800r min-1～2000r min-1, it is 3kW m by power density-2～10kW m-2Microwave irradiation step (1) gained mixed liquor 15min～85min, carry out microwave-assisted graphite powder intercalation oxidation；
(3) joining in ice by step (2) gained reactant liquor, the ice that 1g graphite powder 40ml～150ml water are formed, is 500r min at rotating speed-1～1000r min-1Magnetic agitation under, be hydrolyzed at a temperature of 80 DEG C～100 DEG C reaction 30min～70min；
(4) it is 800r min at rotating speed-1～2000r min-1Magnetic agitation under, by 1g graphite powder use 0.2～2ml weight/mass percentage composition be the H of 30%2O2Consumption, in step (3) gained reactant liquor add H2O2, centrifugation gained precipitate, first with the hydrochloric acid washing precipitate that weight/mass percentage composition is 5～20%, then it is washed with deionized precipitate to pH >=5, it is dried under conditions of less than 100 DEG C, obtains graphite oxide；
(5) step (4) gained graphite oxide is joined ultrasonic stripping in deionized water, 1g graphite oxide deionized water 100ml～350ml, ultrasonic power is 300W～500W, and ultrasonic splitting time is 1h～4h, it is centrifuged off insoluble impurities, obtains graphene oxide colloidal sol.
The method of the present invention is aoxidized by microwave radiation auxiliary graphite intercalation, and not only preparation process is simple, it is often more important that substantially reduce the response time compared with existing synthetic method; and material reaction is abundant; production efficiency is greatly improved, favorable reproducibility, can accomplish scale production.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the graphene oxide of preparation in embodiment 1.
Fig. 2 is transmission electron microscope (TEM) photo of the graphene oxide of preparation in embodiment 1.
Fig. 3 is the XRD figure spectrum of the graphene oxide of preparation in embodiment 2.
Fig. 4 is transmission electron microscope (TEM) photo of the graphene oxide of preparation in embodiment 2.
Fig. 5 is the XRD figure spectrum of the graphene oxide of preparation in embodiment 3.
Fig. 6 is transmission electron microscope (TEM) photo of the graphene oxide of preparation in embodiment 3.
Detailed description of the invention
Further illustrate the present invention below in conjunction with example, but be not intended as the restriction of the present invention.
Embodiment 1
Take 50ml concentrated sulphuric acid in beaker, at ice-water bath and 1000r min-1Being added thereto to 1g crystalline graphite powder and 4g potassium permanganate under stirring condition respectively, be placed in microwave reaction instrument after mixing, controlling stir speed (S.S.) is 1000r min-1, it is 8kW m by power density-2Microwave radiation 40min, then reactant liquor is added in the ice that 50ml water is formed, is 800r min at rotating speed-1Magnetic agitation and 98 DEG C of water bath condition under hydrolysis 30min.Reactant liquor is moved apart water-bath, is 900r min at rotating speed-1Magnetic agitation downhill reaction liquid in drip 0.5ml mass concentration be the H of 30%2O2, centrifugation goes out precipitation, first precipitates twice with salt acid elution that mass concentration is 10%, then is washed with deionized and is precipitated to pH=5.Precipitation is placed in air dry oven, is dried 24h at 90 DEG C, obtains graphite oxide.Weighing 0.3g graphite oxide and join in 100ml distilled water, control ultrasonic power is 400w, ultrasonic stripping 2h, and the insoluble impurity of centrifugal segregation obtains graphene oxide colloidal sol, and graphene oxide yield is 95.4%.The XRD figure spectrum preparing gained graphite oxide is shown in Fig. 1, the characteristic peak of the upper only graphite oxide (001) of its XRD figure spectrum, in 2 θ=11.6 °, the peak of graphite does not occur in 2 θ=26.4 °, illustrates that graphite is fully converted to graphite oxide.Fig. 2 is shown in by the TEM photo preparing gained graphene oxide, is shown as complete lamellar structure.
Embodiment 2
Taking 100ml volume ratio is VConcentrated sulphuric acid:VStrong phosphoric acidThe mixed acid of=9:1 is in beaker, at room temperature and 1800r min-1Being added thereto to 1g crystalline graphite powder and 6g potassium permanganate under stirring condition respectively, be placed in microwave reaction instrument after mixing, controlling stir speed (S.S.) is 1900r min-1, it is 3.8kW m by power density-2Microwave radiation 80min, be then added in the ice that 150ml water is formed, be 1000r min at rotating speed-1Magnetic agitation and 90 DEG C of water bath condition under hydrolysis 60min.Reactant liquor is moved apart water-bath, is 1400r min at rotating speed-1Magnetic agitation downhill reaction liquid in drip 1ml mass concentration be the H of 30%2O2, centrifugation goes out precipitation, first precipitates twice with salt acid elution that mass concentration is 15%, then is washed with deionized and is precipitated to pH=5.Precipitation is placed in air dry oven, is dried 24h at 80 DEG C, arrives to obtain graphite oxide.Weighing 0.4g graphite oxide and join in 100ml distilled water, control ultrasonic power is 500w, ultrasonic stripping 1h, and the insoluble impurity of centrifugal segregation obtains graphene oxide colloidal sol, and graphene oxide yield is 98.1%.The XRD figure spectrum preparing gained graphite oxide is shown in Fig. 3, and Fig. 4 is shown in by the TEM photo preparing gained graphene oxide.
Embodiment 3
Taking 50ml volume ratio is VConcentrated sulphuric acid:VStrong phosphoric acidThe mixed acid of=4:1 is in beaker, at room temperature and 1200r min-1Adding 1g expanded graphite powder and 3g potassium permanganate to it respectively under stirring condition, be placed in microwave reaction instrument after mixing, control stir speed (S.S.) is 1200r/min, is 10kW m by power density-2Microwave radiation 15min, be then added in the ice that 100ml water is formed, be 500r min at rotating speed-1Magnetic agitation and under 80 DEG C of water bath condition hydrolysis 60min.Reactant liquor is moved apart water-bath, is 1800r min at rotating speed-1Magnetic agitation under while stirring in reactant liquor drip 0.2ml mass concentration be the H of 30%2O2, centrifugation, first precipitates twice with salt acid elution that mass concentration is 10%, then is washed with deionized and is precipitated to pH=6.Precipitation is placed in air dry oven, is dried 48h at 60 DEG C, obtains graphite oxide.Weigh 1g graphite oxide adding control ultrasonic power in 100ml water is 500w, and ultrasonic stripping 2h, the undissolved impurity of centrifugal segregation obtains graphene oxide colloidal sol.Graphene oxide yield is 95.0%.The XRD figure spectrum preparing gained graphite oxide is shown in Fig. 5, and Fig. 6 is shown in by the TEM photo preparing gained graphene oxide.
Claims (2)
1. the method that a microwave-assisted prepares graphene oxide, it is characterised in that synthesis step is as follows:
(1) it is 800r min at rotating speed-1~2000r·min-1Magnetic agitation under, graphite powder and strong oxidizer potassium permanganate are added in strong acid mix homogeneously respectively, wherein graphite powder is crystalline graphite powder, natural graphite powder, expanded graphite powder or expansible graphite powder；Potassium permanganate consumption is 1g graphite powder potassium permanganate 3g ~ 6g；Strong acid is commercially available concentrated sulphuric acid, or is the mixed acid of concentrated sulphuric acid and strong phosphoric acid, in mixed acidV Concentrated sulphuric acid :
V Strong phosphoric acidThe mass concentration of >=4:1, concentrated sulphuric acid and strong phosphoric acid is all not less than 92%, and the consumption of acid is 1g graphite powder acid 30ml ~ 100ml；
(2) with microwave irradiation step (1) gained mixed liquor, the oxidation of microwave-assisted graphite powder intercalation is carried out；
(3) joining in ice by step (2) gained reactant liquor, the ice that 1g graphite powder 40ml ~ 150ml water is formed, is 500r min at rotating speed-1~1000r·min-1Magnetic agitation under, be hydrolyzed at a temperature of 80 DEG C ~ 100 DEG C reaction 30 min ~ 70 min；
(4) it is 800r min at rotating speed-1~2000r·min-1Magnetic agitation under, by 1g graphite powder use 0.2ml ~ 2ml weight/mass percentage composition be the H of 30%2O2Consumption, in step (3) gained reactant liquor add H2O2, after being centrifuged gained precipitate separating, then with the hydrochloric acid washing precipitate that weight/mass percentage composition is 5 ~ 20%, finally it is washed with deionized precipitate to pH >=5, it is dried under conditions of less than 100 DEG C, obtains graphite oxide；
(5) step (4) gained graphite oxide is joined ultrasonic stripping in deionized water, 1g graphite oxide deionized water 100ml ~ 350ml, ultrasonic power is 300W ~ 500W, and ultrasonic splitting time is 1h ~ 4h, it is centrifuged off insoluble impurities, obtains graphene oxide colloidal sol.
The method that a kind of microwave-assisted the most as claimed in claim 1 prepares graphene oxide, it is characterised in that in step (2), during with microwave irradiation step (1) gained mixed liquor, need to be 800r min in stir speed (S.S.)-1~2000r·min-1, Microwave Power Density is 3 kW m-2~10 kW·m-2Under conditions of carry out, radiated time is 15min ~ 85min.
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| CN105088391B (en) * | 2015-07-17 | 2017-05-10 | 黑龙江大学 | Poly(p-phenylene vinylene)/graphene composite nanofiber material and preparation method thereof |
| EP3445710A4 (en) * | 2016-04-13 | 2020-01-22 | Green Nanotech Labs, LLC | Low cost and fast method to massively produce graphene and graphene oxide with carbon-rich natural materials |
| CN106082197A (en) * | 2016-06-21 | 2016-11-09 | 哈尔滨工业大学 | A kind of method of microwave Fast back-projection algorithm graphite oxide and application |
| CN107673343A (en) * | 2016-08-02 | 2018-02-09 | 福建新峰二维材料科技有限公司 | A kind of preparation method of graphene nano material |
| CN106477572B (en) * | 2016-10-24 | 2018-08-28 | 上海电力学院 | A kind of method that ultrasonic wave added method prepares graphene oxide |
| CN108101034A (en) * | 2018-01-18 | 2018-06-01 | 莆田市超维二维科技发展有限公司 | A kind of device and method using microwave irradiation one-step method volume production graphene |
| CN109181654B (en) * | 2018-09-13 | 2020-10-30 | 常州德维勒新材料科技有限公司 | Graphene-based composite heat-conducting film and preparation method and application thereof |
| CN112174122A (en) * | 2020-09-30 | 2021-01-05 | 李素红 | Antibacterial graphene nano knife and preparation method and application thereof |
| CN112452686A (en) * | 2020-12-11 | 2021-03-09 | 安徽威能电源科技有限公司 | Surface treatment method for improving antistatic performance of electronic component |
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