CN102173414A - Method for preparing graphene oxide by chemical peeling - Google Patents
Method for preparing graphene oxide by chemical peeling Download PDFInfo
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Abstract
The invention relates to a method for preparing graphene oxide by chemical peeling, belonging to the field of graphene oxide preparation. The method comprises the following steps: (1) graphite oxide preparation: selecting expanded graphite, strong acid, oxidant and distilled water according to the proportion of (0.1-0.8g):(10-90ml):(0.6-12g):(40-300ml); mixing the expanded graphite with the strong acid evenly, adding oxidant and then carrying out a reaction on the mixture for 0.25-4 hours in a condition of 30-45 DEG C; adding distilled water to react for 0.5-2.5 hours and washing the filter cake to neutral with distilled water; rinsing the filter cake with absolute ethyl alcohol, drying the cake in a condition of 30-45 DEG C to obtain the graphite oxide. (2) graphene oxide preparation: selecting the graphite oxide and organic solvent according to the proportion of (0.02-0.1g):(15-70ml); adding the graphite oxide to the solvent and dispersing with a 40-50kHz ultrasonic sound for 0.5-10 hours; centrifugating at a rate of 3000-5000r/min for 20-90 minutes; taking the suspension solution and drying in a condition of 30-45DEG C to obtain the graphene oxide. The method in the invention is safe in operation and has low costs.
Description
Technical field
The invention belongs to the preparation method of graphene oxide, refer to that particularly a kind of chemical stripping prepares the method for graphene oxide.
Background technology
Graphene (graphene) is a kind of carbonaceous novel material by the bi-dimensional cellular shape crystalline network of the tightly packed one-tenth of monolayer carbon atom.It is considered to the basic structural unit of soccerballene, carbon nanotube (CNT), graphite, and is special because of its mechanics, quantum and electrical properties, has become Materials science and Condensed Matter Physics field active research forward position the most.The typical conduction velocity of electronics is 8 * 10 in the Graphene
5M/s is though these are slow more a lot, but much bigger than the electronic conduction speed in the general semi-conductor than the light velocity.Except the electric property excellence, tensile modulus of Graphene (1.01TPa) and ultimate strength (116GPa) are suitable with Single Walled Carbon Nanotube (SWCNT), the good (big (2600m of ~ 3000W/ (mK) and specific surface area of thermal conductivity
2/ g).Its high electronic mobility might have very distinguished using value in fields such as nano electron device, transmitter, electrode of solar battery, transistor and conductive polymerss in addition.
Preparation method of graphene mainly contains micromechanics partition method, epitaxy method and heating SiC method at present.The micromechanics partition method is to select for use a kind of material expanded or rub with the pyrolytic graphite of introducing defective, and the surface of body phase graphite produces the flaky crystal of wadding, contains the Graphene of individual layer in these wad a quilt with cotton flaky crystal.This method is the direct method for preparing the high quality Graphene at present.The shortcoming that this method exists is that productive rate is low, cost is high.The epitaxy method is that carbon atom is being infiltrated more than 1000 ℃ in a kind of rare metal as matrix, be cooled to then about 800 ℃, the carbon atom of Shen Ruing can float over the surface of rare metal again before, and is covered with whole stromal surface, finally forms the Graphene of individual layer.The graphene platelet of this method preparation is often in uneven thickness, and the bonding between Graphene and the matrix can influence the characteristic of carbon-coating.Heating SiC method is the Si(0001 at monocrystalline 6H-SiC) remove Si by pyrolysis on the face and prepare Graphene.Be about to sample (UHV, 1.32 * 10 under high vacuum that the surface obtains after peroxidation or hydrogen etching
-8Pa) be heated to 1000 ℃ to remove the oxide compound of sample surfaces by electron-bombardment.After determining that with Auger electron spectrum the oxide compound on surface is removed fully, temperature is increased to 1250 ~ 1450 ℃ after constant temperature 1 ~ 20min, can form the Graphene of individual layer.This method preparation condition requires harsh, and is not easy to operate.
Therefore, expand the Application Areas of Graphene, it is particularly urgent to seek a kind of graphene preparation method simple to operate, with low cost.
Summary of the invention
Technical problem to be solved by this invention just provides the method that a kind of chemical stripping prepares graphene oxide, makes that the equipment of preparation Graphene is simple, easy handling, with low cost, helps large-scale production.
For solving the problems of the technologies described above, a kind of chemical stripping provided by the invention prepares the method for graphene oxide, comprises the steps:
(1) preparation of graphite oxide:
Press expanded graphite: strong acid: oxygenant: the proportioning of distilled water=0.1 ~ 0.8g:10 ~ 90mL:0.6 ~ 12g:40 ~ 300mL, choose expanded graphite, strong acid, oxygenant and distilled water, standby;
With expanded graphite and strong acid uniform mixing, add oxygenant, under 30 ~ 45 ℃ of temperature, react 0.25 ~ 4h; Add distilled water reaction 0.5 ~ 2.5h then, with distilled water filter cake is cleaned to neutral again; With dehydrated alcohol filter cake is swept away, dry under 50 ~ 75 ℃ of temperature, obtain graphite oxide;
(2) preparation of graphene oxide
Press graphite oxide: the proportioning of organic solvent=0.02 ~ 0.1g:15 ~ 70mL, choose graphite oxide and organic solvent, standby;
Graphite oxide is joined in the organic solvent, with frequency ultra-sonic dispersion 0.5 ~ 10h of 40 ~ 50kHz; Then with 3000 ~ 5000 rev/mins rotating speed, centrifugal treating 20 ~ 90min; It is dry under 50 ~ 70 ℃ of temperature to get the upper strata aaerosol solution, obtains graphene oxide.
In the technique scheme, the strong acid in the described step (1) is the vitriol oil, concentrated nitric acid or the mixture of the two.
In the technique scheme, the oxygenant in the described step (1) is one or more in potassium permanganate, potassium perchlorate, the SODIUMNITRATE.
Further, described oxygenant is a potassium permanganate or when containing potassium permanganate, after reacting 0.25 ~ 4h under 30 ~ 45 ℃ of temperature, adds in the hydrogen peroxide and unreacted potassium permanganate.
In the technique scheme, in the described step (2), organic solvent is N, a kind of in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, tetrahydrofuran (THF), ethanol, ethylene glycol, the acetone.
In the technique scheme, in the described step (1), expanded graphite and strong acid uniform mixing in ice-water bath.
In the technique scheme, react 0.25 ~ 4h under 30 ~ 45 ℃ of temperature in the described step (1) and in water-bath, carry out.
The beneficial effect that chemical stripping of the present invention prepares the method for graphene oxide is:
(1) utilized expanded graphite to prepare graphite oxide, because expanded graphite is easy to disperse, specific surface area is big, the graphite oxide degree of oxidation of preparation is very high;
(2) utilize ultrasonic wave the graphene oxide thin slice can be stripped down from graphite oxide, improved production efficiency.Its principle is: ultrasonic wave is the density interphase eradiation in graphite oxide suspension, solution body is flowed and produce ten hundreds of micro-bubbles, these bubbles form at the negative pressuren zone that the ultrasonic wave longitudinal propagation becomes, growth, and at the zone of positive pressure rapid closing, in the process of this being referred to as " cavitation " effect, the bubble closure can form the instantaneous pressure above 10MPa, the successive high pressure that produces resembles a succession of little " blast " and constantly impacts graphite oxide, thereby can access the graphene oxide thin slice;
(3) the centrifugation operation can be separated graphite oxide and the graphene oxide do not peeled off fully, makes that the extraction of graphene oxide is easier;
(4) low, the operational safety of whole preparation method desired reaction temperature, technology is simple, with low cost, productive rate is higher, is easy to realize large-scale industrial production.
Description of drawings
Fig. 1 be expanded graphite (among the figure a) and the prepared graphite oxide (b among the figure) of the embodiment of the invention 2 and X-ray diffraction (XRD) collection of illustrative plates of graphene oxide (c among the figure).
Fig. 2 and Fig. 3 are transmission electron microscope (TEM) picture of the prepared graphene oxide of the embodiment of the invention 2.
Embodiment
Below in conjunction with accompanying drawing specific embodiments of the invention are described in further detail.
Embodiment 1
(1) preparation of graphite oxide
Get the expanded graphite of 0.1g and vitriol oil uniform mixing in ice-water bath of 10mL, the potassium permanganate that slowly adds 0.6g again, in 30 ℃ water-bath, react 0.25h again, the distilled water reaction 0.5h that adds 40mL then, the 30wt% hydrogen peroxide that adds 5mL again, stir 0.5h, with 5wt% hydrochloric acid soln eccentric cleaning, up to no longer containing SO
4 2-Ion is (with 5wt%Ba (NO
3)
2Solution detects), clean to neutral with distilled water again, promptly obtain the thick graphite oxide filter cake of garnet; With dehydrated alcohol filter cake is swept away, be put in 50 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.02g joins in the ethylene glycol solution of 15mL, disperses 0.5h with the ultrasonic frequency of 40kHz, then with 3000 rev/mins rotating speed, centrifugal treating 20min, decant the upper strata aaerosol solution, place 50 ℃ baking oven dry, obtain the graphene oxide of black.The productive rate of this embodiment is 15%.
Embodiment 2
(1) preparation of graphite oxide
Get the expanded graphite of 0.5g and vitriol oil uniform mixing in ice-water bath of 60mL, the potassium permanganate that slowly adds 12g again, in 35 ℃ water-bath, react 1h again, the distilled water reaction 2h that adds 200mL then, the 30wt% hydrogen peroxide that adds 15mL again, stir 1h, with 5wt% hydrochloric acid soln eccentric cleaning, up to no longer containing SO
4 2-Ion is (with 5wt%Ba (NO
3)
2Solution detects), clean to neutral with distilled water again, promptly obtain bolarious thick graphite oxide filter cake.With dehydrated alcohol filter cake is swept away, be put in 70 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.05g joins the N of 50mL, in the dinethylformamide solution, disperses 3h with the ultrasonic frequency of 50kHz, with 5000 rev/mins rotating speed, centrifugal treating 60min decants the upper strata aaerosol solution then, place 60 ℃ baking oven dry, obtain the graphene oxide of black.The productive rate of this embodiment is 40%, and the graphene oxide thickness that obtains is about 1mm(such as Fig. 1 to Fig. 3).
As shown in Figure 1, X-ray diffraction (XRD) collection of illustrative plates shows that a very sharp-pointed very strong again diffraction peak appears in expanded graphite near 2 θ=26.6 °, pairing interlamellar spacing d ≈ 0.334nm, and expanded graphite is after oxidation, (002) and the characteristic peak of (004) disappear, the distinctive characteristic peak of graphite oxide (001) ° appears in 2 θ=9.9, interlamellar spacing d ≈ 0.889nm, obviously the interlamellar spacing (0.334nm) than expanded graphite standard is big a lot, the degree of oxidation that graphite oxide is described is than higher, during ultrasonic peeling off, help coming off of mono-layer graphite oxide alkene thin slice.Graphene oxide is 23.02 ° of very faint very wide again diffraction peaks of of locating to occur in addition, pairing interlamellar spacing d ≈ 0.386nm, also identical substantially with bibliographical information.But than the big 0.051nm of theoretical value.The increase of thickness, also relevant with functional groups such as the hydroxyl of graphene oxide surface attachment, epoxy group(ing).The diffraction peak of graphene oxide is minimum, and one of reason is because the existence of oxygen-containing functional group has caused the unordered of crystalline structure; Second explanation is because the peeling off of height, and it is extremely meagre to make that the lamella of graphene oxide becomes.
As shown in Figure 2, some folds and folding occurred at the surface and the edge of graphene oxide, and most of graphene oxide thin slice flocks together, just as the paper of a very big gauffer.Fold to occur mainly be in the preparation process of graphene oxide and produce during the TEM test sample preparation.The bright field image among Fig. 3 and the contrast of dark field image are just in time complementary, form mechanism according to diffraction contrast, the diffraction contrast picture that has only the crystal sample to form is just deposited the branch of bright field image and dark field image, and its brightness also is the light and shade counter-rotating, promptly form the contrast complementation, show that graphene oxide is a crystalline structure.
Embodiment 3
(1) preparation of graphite oxide
Get the expanded graphite of 0.2g and the vitriol oil uniform mixing of 10mL, slowly add the concentrated nitric acid of 10mL again, and constantly stir.Next slowly add the potassium permanganate of 5g, in 38 ℃ water-bath, react 2h.The distilled water that adds 100mL then reacts 1h, adds the 30wt% hydrogen peroxide of 5mL again, stirs 2h, with 5wt% hydrochloric acid soln eccentric cleaning, up to no longer containing SO
4 2-Ion is (with 5wt%Ba (NO
3)
2Solution detects), clean to neutral with distilled water again, promptly obtain bolarious thick graphite oxide filter cake.With dehydrated alcohol filter cake is swept away, be put in 65 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.08g joins in the ethanolic soln of 60mL, ultrasonic frequency with 40kHz is disperseed 4h, with 4000 rev/mins speed centrifugal treating 30min, decants the upper strata aaerosol solution then, place 70 ℃ baking oven dry, obtain the graphene oxide of black.The productive rate of this embodiment is 30%.
Embodiment 4
(1) preparation of graphite oxide
Get the expanded graphite of 0.8g and vitriol oil uniform mixing in ice-water bath of 90mL, the SODIUMNITRATE that adds 0.6g then, the potassium permanganate that slowly adds 10g again, in 40 ℃ water-bath, react 4h again, the distilled water that adds 300mL then reacts 2.5h, adds the 30 wt% hydrogen peroxide of 15mL again, stirs 3h, with 5wt% hydrochloric acid soln eccentric cleaning, up to no longer containing SO
4 2-Ion is (with 5wt%Ba (NO
3)
2Solution detects), clean to neutral with distilled water again, promptly obtain bolarious thick graphite oxide filter cake; With dehydrated alcohol filter cake is swept away, be put in 60 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.06g joins in the tetrahydrofuran solution of 40mL, ultrasonic frequency with 50kHz is disperseed 7h, with 4500 rev/mins speed centrifugal treating 40min, decants the upper strata aaerosol solution then, place 60 ℃ baking oven dry, obtain the graphene oxide of black.The productive rate of this embodiment is 20%.
Embodiment 5
(1) preparation of graphite oxide
Get the expanded graphite of 0.4g and vitriol oil uniform mixing in ice-water bath of 30mL, slowly add the potassium perchlorate of 2g again, in 45 ℃ water-bath, react 3h again, add the distilled water reaction 2.5h of 150mL then, with 5wt% hydrochloric acid soln eccentric cleaning, up to no longer containing SO
4 2-(with 5wt%Ba (NO
3)
2Solution detects), clean to neutral with distilled water again, promptly obtain bolarious thick graphite oxide filter cake; With dehydrated alcohol filter cake is swept away, be put in 55 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.1g joins in the N-N-methyl-2-2-pyrrolidone N-solution of 70mL, ultrasonic frequency with 40kHz is disperseed 10h, then with 3800 rev/mins speed centrifugal treating 90min, decant the upper strata aaerosol solution, place 60 ℃ baking oven dry, obtain the graphene oxide of black, the productive rate of this embodiment is 25%.
Embodiment 6
(1) preparation of graphite oxide
Getting the expanded graphite of 0.6g and the concentrated nitric acid of 50mL mixes in ice-water bath, the potassium permanganate that slowly adds 10g, in 32 ℃ water-bath, react 0.5h again, the distilled water reaction 2h that adds 250mL then, the 30 wt% hydrogen peroxide that add 15mL again, stir 2h, clean to neutral with distilled water again, promptly obtain bolarious thick graphite oxide filter cake; With dehydrated alcohol filter cake is swept away, be put in 75 ℃ the baking oven dryly, obtain the graphite oxide of black;
(2) preparation of graphene oxide
The graphite oxide of getting 0.04g joins in the acetone of 30mL, ultrasonic frequency with 50kHz is disperseed 6h, then with 3500 rev/mins speed centrifugal treating 70min, decant the upper strata aaerosol solution, place 70 ℃ baking oven dry, obtain the graphene oxide of black, the productive rate of this embodiment is 35%.
The method that chemical stripping of the present invention prepares graphite oxide has been improved the preparation technology of graphene oxide, make the technology of further preparation Graphene and graphene oxide matrix material easier, also make the making of graphene nano electron device become possibility, Graphene also can be used to prepare nanocomputer chip, electrode of solar battery, transmitter, electrical condenser, hydrogen storage material, a ballistic transistor simultaneously, and be applied to military industry fields such as guided missile precise guidance and missile intercept, all have very important application value.
Core of the present invention is to utilize the mode of chemical stripping to prepare graphene oxide, therefore, on the basis of the principle of the invention, utilizes the chemical stripping legal system to be equipped with graphene oxide, and then prepares the method for Graphene, all belongs to protection scope of the present invention.
Claims (9)
1. a chemical stripping prepares the method for graphene oxide, it is characterized in that it comprises the steps:
(1) preparation of graphite oxide:
Press expanded graphite: strong acid: oxygenant: the proportioning of distilled water=0.1 ~ 0.8g:10 ~ 90mL:0.6 ~ 12g:40 ~ 300mL, choose expanded graphite, strong acid, oxygenant and distilled water, standby;
With expanded graphite and strong acid uniform mixing, add oxygenant, under 30 ~ 45 ℃ of temperature, react 0.25 ~ 4h; Add distilled water reaction 0.5 ~ 2.5h then, with distilled water filter cake is cleaned to neutral again; With dehydrated alcohol filter cake is swept away, dry under 50 ~ 75 ℃ of temperature, obtain graphite oxide;
(2) preparation of graphene oxide
Press graphite oxide: the proportioning of organic solvent=0.02 ~ 0.1g:15 ~ 70mL, choose graphite oxide and organic solvent, standby;
Graphite oxide is joined in the organic solvent, with frequency ultra-sonic dispersion 0.5 ~ 10h of 40 ~ 50kHz; Then with 3000 ~ 5000 rev/mins rotating speed, centrifugal treating 20 ~ 90min; It is dry under 50 ~ 70 ℃ of temperature to get the upper strata aaerosol solution, obtains graphene oxide.
2. a kind of chemical stripping according to claim 1 prepares the method for graphene oxide, it is characterized in that: the strong acid in the described step (1) is the vitriol oil, concentrated nitric acid or the mixture of the two.
3. a kind of chemical stripping according to claim 1 and 2 prepares the method for graphene oxide, it is characterized in that: the oxygenant in the described step (1) is one or more in potassium permanganate, potassium perchlorate, the SODIUMNITRATE.
4. a kind of chemical stripping according to claim 3 prepares the method for graphene oxide, it is characterized in that: described oxygenant is a potassium permanganate or when containing potassium permanganate, after reacting 0.25 ~ 4h under 30 ~ 45 ℃ of temperature, add in the hydrogen peroxide and unreacted potassium permanganate.
5. a kind of chemical stripping according to claim 1 and 2 prepares the method for graphene oxide, it is characterized in that: in the described step (2), organic solvent is N, a kind of in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, tetrahydrofuran (THF), ethanol, ethylene glycol, the acetone.
6. a kind of chemical stripping according to claim 3 prepares the method for graphene oxide, it is characterized in that: in the described step (2), organic solvent is N, a kind of in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, tetrahydrofuran (THF), ethanol, ethylene glycol, the acetone.
7. a kind of chemical stripping according to claim 4 prepares the method for graphene oxide, it is characterized in that: in the described step (2), organic solvent is N, a kind of in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, tetrahydrofuran (THF), ethanol, ethylene glycol, the acetone.
8. a kind of chemical stripping according to claim 1 and 2 prepares the method for graphene oxide, it is characterized in that: in the described step (1), and expanded graphite and strong acid uniform mixing in ice-water bath.
9. a kind of chemical stripping according to claim 1 and 2 prepares the method for graphene oxide, it is characterized in that: react 0.25 ~ 4h under 30 ~ 45 ℃ of temperature in the described step (1) and carry out in water-bath.
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