CN101591014A - A kind of method of realizing large-scale preparation of monolayer oxidized graphene - Google Patents
A kind of method of realizing large-scale preparation of monolayer oxidized graphene Download PDFInfo
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Abstract
The present invention relates to a kind of method of realizing large-scale preparation of monolayer oxidized graphene.Concrete steps are, with oxygenant natural flake graphite are carried out oxidation, obtain graphite oxide, after ultrasonic wave is peeled off, remove by filter unreacted graphite, get the aqueous solution of graphene oxide, add flocculation agent, after sedimentation, filtration, drying, obtain the graphene oxide solid.The present invention can separate the graphene oxide solid at an easy rate by flocculating settling from its aqueous dispersions, thereby has realized the mass preparation of Graphene; Raw materials cost is cheap to be easy to get, processing ease, simple, the favorable reproducibility of technology, can carry out large-scale industrial production.With the monatomic graphene oxide of the present invention's preparation, can make the flake reinforced phase of matrix material, preparation has the material of strong mechanical performance and barrier property; Can be used to make fingerprint collecting material etc.Its reduzate---Graphene can be used for constructing the sub-components and parts of 2 D photoelectric such as nano level computer chip, electrode of solar battery and field-effect transistor.
Description
Technical field
The present invention relates to a kind of method of realizing large-scale preparation of monolayer oxidized graphene.
Background technology
2004, single-layer graphene crystal (Geim, A.K.et al.Scienc, 306 are peeled off and observed to a kind of very simple method of usefulness such as the physics professor Geim of Univ Manchester UK, 666 (2004)), caused " carbon " upsurge of scientific circles' new rounds.The theoretical specific surface area of Graphene is up to 2600m2/g (Chae, H.K.etal.Nature, 427,523 (2004)), have outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060GPa) (Schadler, L.S.et al.Appl Phys Lett, 73,3842 (1998)), and high speed electronic mobility (15000cm2/ (Vs)) (Zhang under the room temperature, Y.et al.Nature, 438,201 (2005)).The special construction of Graphene, a series of character such as specific conductivity (Novoselov, K.S.et al.Nature, 38,197 (2005)) that make it have perfect quantum tunneling effect, half integral quantum hall effect and never disappear.These particular performances make it have broad application prospects in fields such as Materials science and electronics.
At present, preparation method of graphene has: mechanically peel method, chemical Vapor deposition process, graft process and oxidation-reduction method.The Graphene that wherein preceding two kinds of methods obtain yields poorly, and contains a large amount of multiwalled Graphenes in the product of graft process, and these have all limited it to a certain extent in each field, particularly the application aspect matrix material.Oxidation-reduction method is to be raw material with the natural flake graphite, is that starting point prepares Graphene from the preparation graphene oxide.And global graphite is rich in minerals, and China also is graphite high yield state.Therefore this method is just laid a good foundation for the mass preparation of Graphene from the raw material aspect.So prepare the strategic starting point that graphene oxide is extensive synthesizing graphite alkene from graphite.And compare with carbon nanotube with the soccerballene of costliness, graphene oxide is cheap, and raw material is easy to get; Also contain a large amount of-OH and-COOH group on the graphene oxide, can carry out various chemical modifications at an easy rate, be expected to become the high quality filler of polymer nanocomposites.
Oxidation-reduction method mainly is to utilize strong oxidizer that natural flake graphite is carried out obtaining graphene oxide after the oxidation, obtains Graphene through reduction again.Yet the resulting graphene oxide of this method is a kind of two-dimensional slice shape structure, good film-forming property, and good dispersity in water adopts methods such as common suction filtration, centrifugal settling, evaporation to be difficult to graphene oxide is separated from its aqueous solution.Particularly to large-scale industry preparation with handle, these method cost height, efficient are low, should not apply.Therefore explore a kind ofly simply be suitable for, the method for a large amount of graphene oxides of preparation of economical and efficient, thereby solve the mass preparation of Graphene, the widespread use that realizes Graphene is had crucial value.
Summary of the invention
The objective of the invention is at above-mentioned present situation, aim to provide that a kind of raw materials cost cheaply is easy to get, processing ease, simple, the favorable reproducibility of technology, but the method for preparing mono-layer graphite oxide alkene of heavy industrialization.
The implementation of the object of the invention is, a kind of method of realizing large-scale preparation of monolayer oxidized graphene, and concrete steps are as follows:
1. graphite oxidation: with 2 grams-500 gram natural flake graphites is raw material, uses the oxygenant oxidation, and oxidation is after 72 hours-100 hours, and oxide compound is washed till neutrality with 1 liter of deionized water wash suction filtration, obtains graphite oxide after the drying,
Described oxygenant is nitration mixture and other combination of agents thing of 35 milliliters of vitriol oils and 18 milliliters of concentrated nitric acids, other reagent is one or more the combination in Potcrate, potassium permanganate, Vanadium Pentoxide in FLAKES, Potassium Persulphate, the hydrogen peroxide, the dosage of other reagent is 10 grams-22 grams
2. disperse to peel off: the oxidation graphite solid after depickling is washed joins immediately and is diluted to concentration in the deionized water is 0.5 grams per liter, disperseed to peel off 0.5 hour to 10 hours with ultrasonic wave, filter unreacted graphite then, collect filtrate, obtain the aqueous solution of graphene oxide, unreacted graphite repeating step is 2. operation 1.
3. flocculating settling: in the aqueous solution of graphene oxide, add flocculation agents, graphene oxide is settled down, filter then, obtain the graphene oxide solid after the filter cake lyophilize by 5 grams to the amount of 50 grams per liter graphite oxide aqueous solutions,
Described flocculation agent is one or more the combination in potassium hydroxide, sodium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, Repone K, sodium-chlor, sodium sulfate, potassiumiodide or the polyacrylamide.
The present invention can separate the graphene oxide solid at an easy rate by flocculating settling from its aqueous dispersions, thereby has realized the mass preparation of Graphene; Raw materials cost is cheap to be easy to get, processing ease, simple, the favorable reproducibility of technology, can carry out large-scale industrial production.
With the monatomic graphene oxide of the present invention's preparation, can be used as the flake reinforced phase of matrix material, preparation has the high mechanical property and the material of barrier property; Can be used to make fingerprint collecting material etc.Its reduzate-Graphene can be used for constructing the sub-components and parts of 2 D photoelectric such as nano level computer chip, electrode of solar battery and field-effect transistor, has extremely important actual application value.
Description of drawings
Fig. 1 is the process flow diagram of mass preparation graphene oxide,
Fig. 2 is the photo of flocculation step in the preparation graphene oxide technology, and wherein a is the aqueous solution of graphene oxide; B is for adding the settled photo of flocculation agent rear oxidation Graphene; C is the graphene oxide solid after the filtering and washing, the picture that inserts among the c be the graphene oxide solid dispersed that obtains in water,
Fig. 3 a, b are field emission low resolution, the high resolution scanning electron microscope pictures of monoatomic layer graphene oxide,
Fig. 4 a, b are high resolution transmission low resolution, the high resolution electron microscope (HREM) pictures of monoatomic layer graphene oxide,
Fig. 5 a, b, c, d are that the thickness of monoatomic layer graphene oxide is atomic force microscope picture and the cross-sectional analysis of 0.730nm, 0.826nm,
Fig. 6 is the X-ray diffraction spectrogram of monoatomic layer graphene oxide,
Fig. 7 is the Fourier transform infrared spectroscopy figure of monoatomic layer graphene oxide.
Embodiment
With reference to Fig. 1, concrete steps of the present invention are with oxygenant natural flake graphite to be carried out oxidation, obtain graphite oxide, after ultrasonic wave is peeled off, remove by filter unreacted graphite, obtain the aqueous solution of graphene oxide, add flocculation agent, after sedimentation, filtration, drying, obtain the graphene oxide solid.
Oxygenant is best for being the vitriol oil, concentrated nitric acid nitration mixture and other combination of agents thing, and other reagent the best is one or more the combination in Potcrate, potassium permanganate, the Vanadium Pentoxide in FLAKES.Oxidization time the best of oxygenant is 72 hours to 96 hours.Ultra-sonic dispersion splitting time the best is 1 hour to 2 hours.Flocculation agent the best is one or more the combination in potassium hydroxide, sodium hydroxide, hydrochloric acid, Repone K, the sodium-chlor.
The graphene oxide of the present invention's preparation is made up of carbon atom, and area is for to be that the small size single thin layer sheet structure of square micron level, visual inspection are the dark-brown powder.Field emission scanning electron microscope photo (shown in Fig. 3 a, b), high resolution transmission electron microscopy photo Fig. 4 a, b, show the graphene oxide with flaky texture in conjunction with atomic force microscope photo Fig. 5 a, b, its thickness is several nanometers at zero point, is monoatomic layer thickness.X-ray diffraction spectrum demonstrates the diffraction peak of graphene oxide as shown in Figure 6: the diffraction peak of 2 θ=10.12 ° and mono-layer graphite oxide alkene structure: 2 θ=29 °, 30.8 °.Fourier transformation safflower external spectrum as shown in Figure 7, the characteristic peak of some groups is produced by oxidising process as can be seen.Each peak is respectively C-O:1053cm-1, C-O-C:1280cm-1, C-OH:1385cm-1, and C=O:1723cm-1.Peak about 1631cm-1 is the skeletal vibration of Graphene.
Below, in conjunction with the accompanying drawings and embodiments the present invention is described in more detail.
Second step, dispersion are peeled off: the graphite oxide after will washing is added in the deionized water immediately, and being diluted to concentration is 0.5 grams per liter, after the dilution, disperses to peel off 1 hour with ultrasonic wave.Remove by filter unreacted graphite then, collect filtrate, obtain the aqueous solution of the graphene oxide shown in Fig. 2 a, solution in the small beaker is: the later solution of adding 50 ml deionized water dilution in 10 milliliters of large beakers, graphene oxide dispersed fine in water as we can see from the figure.
The 3rd step, flocculating settling, filtration, drying: add 5 gram sodium hydroxide solutions as flocculation agent in the aqueous solution of graphene oxide, graphene oxide is separated out sedimentation with floss at once, and after leaving standstill, graphene oxide settles down fully.Obtain 2.3 gram graphene oxide solids (shown in Fig. 2 b, c) at last after filtration, the drying.
Embodiment 2, the preparation method who presses embodiment 1, be described oxygenant be 10 the gram potassium permanganate, obtain the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 3, the preparation method who presses embodiment 1, be described oxygenant be 15 the gram Potassium Persulphates, obtain the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 6 presses the preparation method of embodiment 1, be described oxygenant be 10 the gram potassium permanganate and 1.7 the gram Potassium Persulphates, obtain the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 7, the preparation method who presses embodiment 1, oxidization time is 72 hours, obtains the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 8, the preparation method who presses embodiment 1, the ultrasonic wave splitting time is 0.5 hour, obtains the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 9, the preparation method who presses embodiment 1, flocculation agent is a hydrochloric acid soln, obtains the result shown in Fig. 2 b, c equally.
Embodiment 18, the preparation method who presses embodiment 1 are the combination that described flocculation agent is changed to potassium hydroxide and sodium-chlor, obtain the result shown in Fig. 2 b, c equally.
Embodiment 19, the preparation method who presses embodiment 1, flocculation agent is the composition of hydrochloric acid and sodium-chlor, the ratio of hydrochloric acid and sodium-chlor is 1: 1, obtains the result shown in Fig. 2 b, c equally.
Embodiment 21, the preparation method who presses embodiment 1,50 gram natural flake graphites under agitation are distributed in the nitration mixture of 35 milliliters of vitriol oils and 18 milliliters of concentrated nitric acids, obtain the result shown in Fig. 3,4,5,6,7 equally.
Embodiment 22, the preparation method who presses embodiment 1 ~ 15,500 gram natural flake graphites under agitation are distributed in the nitration mixture of 35 milliliters of vitriol oils and 18 milliliters of concentrated nitric acids, oxidization time is 100 hours, the ultrasonic wave splitting time is 10 hours, the consumption of flocculation agent is 50 grams per liter graphite oxide aqueous solutions, obtains the result shown in Fig. 2 b, c and Fig. 3,4,5,6,7 equally.
Claims (5)
1, a kind of method of realizing large-scale preparation of monolayer oxidized graphene is characterized in that concrete steps are as follows:
1. graphite oxidation: with 2 grams-500 gram natural flake graphites is raw material, uses the oxygenant oxidation, and oxidation is after 72 hours-100 hours, and oxide compound is washed till neutrality with 1 liter of deionized water wash suction filtration, obtains graphite oxide after the drying,
Described oxygenant is nitration mixture and other combination of agents thing of 35 milliliters of vitriol oils and 18 milliliters of concentrated nitric acids, other reagent is one or more the combination in Potcrate, potassium permanganate, Vanadium Pentoxide in FLAKES, Potassium Persulphate, the hydrogen peroxide, the dosage of other reagent is 10 grams-22 grams
2. disperse to peel off: the oxidation graphite solid after depickling is washed joins immediately and is diluted to concentration in the deionized water is 0.5 grams per liter, disperseed to peel off 0.5 hour to 10 hours with ultrasonic wave, filter unreacted graphite then, collect filtrate, obtain the aqueous solution of graphene oxide, unreacted graphite repeating step is 2. operation 1.
3. flocculating settling: in the aqueous solution of graphene oxide, add flocculation agents, graphene oxide is settled down, filter then, obtain the graphene oxide solid after the filter cake lyophilize by 5 grams to the amount of 50 grams per liter graphite oxide aqueous solutions,
Described flocculation agent is one or more the combination in potassium hydroxide, sodium hydroxide, hydrochloric acid, sulfuric acid, nitric acid, Repone K, sodium-chlor, sodium sulfate, potassiumiodide or the polyacrylamide.
2, press the method for the described a kind of realizing large-scale preparation of monolayer oxidized graphene of claim 1, it is characterized in that oxygenant is the vitriol oil, concentrated nitric acid nitration mixture and combination of agents thing, reagent is one or more the combination in Potcrate, potassium permanganate, the Vanadium Pentoxide in FLAKES.
3, by the method for the described a kind of realizing large-scale preparation of monolayer oxidized graphene of claim 1, the oxidization time that it is characterized in that described oxygenant is 72 hours to 96 hours.
4, by the method for the described a kind of realizing large-scale preparation of monolayer oxidized graphene of claim 1, it is characterized in that described ultra-sonic dispersion splitting time is 1 hour to 2 hours.
5,, it is characterized in that flocculation agent is one or more the combination in potassium hydroxide, sodium hydroxide, hydrochloric acid, Repone K, the sodium-chlor by the method for the described a kind of realizing large-scale preparation of monolayer oxidized graphene of claim 1.
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