CN108394897A - A kind of magnanimity preparation method of porous oxidation graphene - Google Patents
A kind of magnanimity preparation method of porous oxidation graphene Download PDFInfo
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- CN108394897A CN108394897A CN201810516090.8A CN201810516090A CN108394897A CN 108394897 A CN108394897 A CN 108394897A CN 201810516090 A CN201810516090 A CN 201810516090A CN 108394897 A CN108394897 A CN 108394897A
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Abstract
The present invention provides a kind of magnanimity preparation methods of porous oxidation graphene.The magnanimity preparation method of porous oxidation graphene of the present invention includes the following steps：1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is prepared into graphene oxide water solution；2) by graphene oxide water solution ultrasonic disperse, finely dispersed graphene oxide water solution is obtained；3) cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution, obtains graphene oxide ice cube；4) graphene oxide ice cube is freeze-dried, obtains the porous oxidation graphene.The magnanimity preparation method of the porous oxidation graphene of the present invention, operating procedure is simple, it is at low cost, the additive additional without adding etching agent etc., porous oxidation graphene uniform component obtained, and aperture-controllable, in 1~20 μ m, pore size distribution range is big, is suitable for the magnanimity industrial production of porous oxidation graphene.
Description
Technical field
The invention belongs to the preparing technical fields of porous oxidation graphene, are related to a kind of magnanimity system of porous oxidation graphene
Preparation Method.
Background technology
Graphene is a kind of crystal with two-dimensional structure, passes through sp by single layer of carbon atom2Hydridization forms two-dimentional six side bees
Nest shape lattice structure and constitute.So single-layer graphene material is only current there are one the theoretic throat (0.335nm) of carbon atom
Most thin substance in known two-dimensional material.Its unusual physics is determined just because of unique crystal structures possessed by graphene
Performance, such as high intensity and hardness, huge specific surface area, excellent heat transfer, strong electric conductivity and high carrier mobility
And good optical characteristics.There are many excellent characteristics just because of graphene so that it can be widely applied to flexibility
The necks such as electronic device, high-precision gas sensor, biosensor, catalyzed conversion, composite material, battery and ultracapacitor
Domain.
Because there is very high Van der Waals force and strong π-π active forces in its piece interlayer in single graphene so that graphene
The characteristics of layer is accumulated with interlayer, and easily reunion can not disperse, cannot give full play to its large specific surface area in water.In order to effective
It solves the problems, such as that graphene is reunited and processed in water, chemical oxidation stripping is carried out to graphene, obtained graphene oxide tool
Have amphipathic so that graphene solution has machinability, is more suitable for industrial manufacture.In addition, being carried out to graphene oxide more
Hole is modified the utilization rate that can significantly improve its surface area, to give full play to the advantage of two-dimensional layer material.
Graphene oxide (Graphene Oxide, abbreviation GO) is the important forerunner that chemical method prepares graphene
Body.The surface of graphene oxide has a certain amount of carboxyl, carbonyl, epoxy group and hydroxy functional group, leads to graphene oxide sheet
Layer structure is changed and defect occurs, to show the physical and chemical performance different from the graphene of homogeneous structural.With functional group
Graphene oxide can be uniformly dispersed in many solvents, can be good at being applied to the fields such as catalysis, dispersing aid.
The preparation method of existing porous oxidation graphene has electron beam lithography, MnO2Chemical etching, ultraviolet radiant light are anti-
The methods of answer.But the complex process that electron beam lithography and ultraviolet radiant light reaction method are related to is cumbersome, MnO2Chemical etching
Rule can introduce impurity, seriously limit the subsequent applications of this novel graphite alkene derived material porous oxidation graphene.
CN107720743A discloses a kind of controllable method for preparing of two-dimentional porous structure graphene oxide：By ammonium persulfate
It is added in graphene oxide dispersion, wherein the mass ratio of ammonium persulfate and graphene oxide is 5~11:1, it is heated to reflux,
Cooled to room temperature obtains two-dimentional porous structure stannic oxide/graphene nano material.The two-dimentional porous structure oxygen that the invention obtains
Specific surface area and pore volume the ratio graphene oxide of graphite alkene significantly increase, but introduce ammonium sulfate in preparation process etc. and is miscellaneous
Matter, the bad control in aperture of the porous oxidation graphene of preparation.
CN105692598A discloses a kind of preparation method of lamella porous oxidation graphene, includes the following steps：1) will
Graphene oxide and binder are dissolved in the water, and are made into precursor solution；2) by the precursor solution be placed in container into
The two-way frost reaction of row, obtains intermediate product；The bottom of the container has Wedge device；3) centre for obtaining step 2)
Product is freeze-dried to remove solvent, obtains lamella porous oxidation graphene.The preparation method of the invention can be prepared not
With the graphene oxide of interlamellar spacing and the lamella porous structure in aperture, size, porosity and the hole shape of this outer plies porous structure
Looks can also be adjusted on a large scale, still, in preparation process need to add binder, impurity have also been introduced, and this method needs a constant temperature
Degree makes solvent volatilize, and manufacturing cost is relatively high.
CN102963886A discloses a kind of preparation method of cellular graphene oxide, is as follows：(1) with day
Right crystalline flake graphite is raw material, and graphite oxide is prepared using hunmers methods；(2), graphite oxide obtained above at 10~50 DEG C
Under, disperse 10~30min using magnetic stirring apparatus, is configured to mixed uniformly suspension；(3), prepared oxidation is measured
Graphite suspension 0.1mg/ml~1mg/ml is added in the cuboid electrolytic cell cleaned up, is then placed in graphite electrode
Two insides of electrolytic cell；(4), make graphite oxide stripping at single-layer graphene oxide with alternating electric field, stripping voltage for 10V~
30V, stripping frequency are 50~5000Hz, and action time is 30~120min.The invention is peelable to prepare cellular graphite oxide
The method of alkene removes graphite oxide with alternating electric field, compares traditional ultrasonic stripping method, have many advantages, such as that noiseless, yield is high,
But the preparation of cellular graphene oxide needs to be equipped with special consersion unit, is unfavorable for the large quantities of of cellular graphene oxide
Amount production.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of magnanimity preparation sides of porous oxidation graphene
Method, the method operating procedure is simple, at low cost, the additive additional without adding etching agent etc., porous oxidation graphene obtained
Uniform component, and aperture-controllable, in 1~20 μ m, pore size distribution range is big, is suitable for the magnanimity of porous oxidation graphene
Industrial production.
For this purpose, the present invention uses following technical scheme：
A kind of magnanimity preparation method of porous oxidation graphene, the magnanimity preparation method include the following steps：
1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is prepared
Graphene oxide water solution；
2) by graphene oxide water solution ultrasonic disperse made from step 1), it is water-soluble to obtain finely dispersed graphene oxide
Liquid；
3) cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution made from step 2), is aoxidized
Graphene ice cube；
4) the graphene oxide ice cube that step 3) obtains is freeze-dried, obtains the porous oxidation graphene.
The present invention prepares graphene oxide by Hummers improved methods, prepares graphene oxide water solution through ultrasonic disperse
After obtain finely dispersed graphene oxide water solution, cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution
In obtain graphene oxide ice cube, graphene oxide ice cube is freeze-dried, porous oxidation graphene is obtained.In this method
Be not introduced into other additives, etching agent be not added and avoids introducing impurity, be not added solvent avoid pyroreaction will be molten
Agent is volatilized, and is to obtain porous oxidation graphene by cryogenic liquid and freeze-drying, simpler in technique, production efficiency is more
Height is not necessarily to special or complex reaction equipment, and cost is lower, porous oxidation graphene uniform component obtained, and aperture-controllable
In 1~20 μ m, pore size distribution range is big, is suitable for the magnanimity industrial production of porous oxidation graphene；That prepares is porous
Graphene oxide contains the characteristics of compared with polyfunctional group, be convenient for subsequent functional modification, can be used for electro-catalysis, ultracapacitor,
The fields such as lithium ion battery and organic catalysis.
In step 3), the cryogenic liquid is that room temperature is gaseous cryogenic liquid；Preferably, the cryogenic liquid is liquid nitrogen
Or dry ice.
In step 3), the cryogenic liquid be poured slowly into finely dispersed graphene oxide water solution rate be 3~
100mL/min, such as it is 3,10mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/ to pour into rate
Min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, preferably 40~60mL/min.If cryogenic liquid falls
Enter that rate is too fast, if the rate of pouring into of cryogenic liquid is higher than 100mL/min, makes the hole knot of porous oxidation graphene obtained
Structure is imperfect, and lamellar graphite alkene is crushed under liquid nitrogen gasification impact force and forms fibrous material；If the importing speed of cryogenic liquid
Rate is too slow, then so that cryogenic liquid is vaporized quickly, does not have the purpose of fast cooling, cause graphene oxide can not pore-forming, therefore
Cryogenic liquid need to rationally be controlled pours into rate.
In step 4), the freeze-drying is vacuum freeze drying；Preferably, the temperature of the freeze-drying be -40~-
60 DEG C, such as the temperature of freeze-drying is -40 DEG C, -45 DEG C, -50 DEG C, -55 DEG C, -60 DEG C；The time of the freeze-drying is 12
~48h, for example, freeze-drying time be 12h, 15h, 16h, 18h, 20h, for 24 hours, 25h, 30h, 35h, 36h, 40h, 48h.
Graphene oxide (abbreviation GO) is generally aoxidized through strong acid by graphite and is obtained.There are mainly three types of the sides for preparing graphite oxide
Method：Brodie methods, Staudenmaier methods and Hummers methods.Wherein, the timeliness of the preparation process of Hummers methods is relatively
It is also relatively safer in good and preparation process, it is current most common one kind.Hummers methods use the potassium permanganate in the concentrated sulfuric acid
With powdered graphite is oxidized react after, obtain brown edge have derivative carboxylic acid group and in the plane be mainly phenolic hydroxyl group and
The graphite flake of epoxy group, it is graphene oxide that this graphene layers can be vigorously stirred stripping through ultrasound or high shear, and
Stable, sundown single-layer graphene oxide suspension is formed in water.
The application prepares graphene oxide using Hummers improved methods, of the invention relative to conventional Hummers methods
Hummers improved methods are than the former less impurity and reduce the NO generated in reaction2、N2O4Equal toxic gases.
In step 1), the Hummers improved methods include the following steps：It is prepared and is mixed as raw material using the concentrated sulfuric acid and concentrated phosphoric acid
Acid solution prepares graphene oxide using graphite, mixed acid solution, potassium permanganate as raw material.
Preferably, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is (8~10) in the mixed acid solution:1, for example, the concentrated sulfuric acid and
The volume ratio of concentrated phosphoric acid is 8:1、9:1、10:1, preferably 9:1；The graphite, mixed acid solution, potassium permanganate mass ratio be
1:(180~185):(5~8), preferably 1:182.5:6.
The preparation process of graphene oxide described in step 1) is：
A) by H2SO4And H3PO4It is by volume (8~10):1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation keeps its mixing equal at room temperature
It is even；By the single-necked flask with mixed liquor as under ice-water bath, and it is slowly added to potassium permanganate thereto, magnetic agitation reaction 1
~2h, wherein the mass ratio of the graphite, mixed acid solution, potassium permanganate is 1:(180~185):(5~8)；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, it then will reaction
Liquid is poured in the ice water containing 100mL, and hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；Reaction
After complete, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
To the graphene oxide.
Preferably, the specific preparation process of graphene oxide described in step 1) is：
A) by H2SO4And H3PO4It is 9 by volume:1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation keeps its mixing equal at room temperature
It is even；By the single-necked flask with mixed liquor as under ice-water bath, and it is slowly added to potassium permanganate thereto, magnetic agitation reaction
1h, wherein the mass ratio of the graphite, mixed acid solution, potassium permanganate is 1:182.5:6；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, it then will reaction
Liquid is poured in the ice water containing 100mL, and hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；Reaction
After complete, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
To the graphene oxide.
In step 1), the molar concentration of the graphene oxide water solution is 0.001~20mg/mL, the graphite oxide
The molar concentration of aqueous solution determines the size in hole, if the molar concentration of graphene oxide water solution is less than 0.001mg/mL,
Then cause aperture too big or hole rupture and do not become incomplete hole, if the molar concentration of graphene oxide water solution is more than
20mg/mL then causes graphene oxide to occur to reunite or do not become hole；Therefore rubbing for graphene oxide water solution need to rationally be controlled
Your concentration, for example, the molar concentration of the graphene oxide water solution is 0.001mg/mL, 0.005mg/mL, 0.01mg/mL,
0.02mg/mL、0.05mg/mL、0.08mg/mL、0.1mg/mL、0.2mg/mL、0.3mg/mL、0.4mg/mL、0.5mg/mL、
0.6mg/mL、0.7mg/mL、0.8mg/mL、0.9mg/mL、1mg/mL、2mg/mL、3mg/mL、4mg/mL、5mg/mL、6mg/
mL、7mg/mL、8mg/mL、9mg/mL、10mg/mL、11mg/mL、12mg/mL、13mg/mL、14mg/mL、15mg/mL、16mg/
mL、17mg/mL、18mg/mL、19mg/mL、20mg/mL。
Preferably, the molar concentration of the graphene oxide water solution is 1~10mg/mL.
In step 2), the purpose of ultrasonic disperse is to avoid the reunion of graphene oxide, convenient for step 3) and step 4) at
Hole, the frequency of the ultrasonic disperse are 15~25KHz, for example, the frequency of ultrasonic disperse is 15KHz, 16KHz, 17KHz, 18KHz,
19KHz、20KHz、21KHz、22KHz、23KHz、24KHz、25KHz；The time of the ultrasonic disperse is 150~200min, example
If the time of ultrasonic disperse is 150min, 160min, 170min, 180min, 190min, 200min.
The aperture of porous oxidation graphene of the present invention is 1~20 μm, such as the aperture of porous oxidation graphene is 1 μ
m、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μ
m、19μm、20μm。
As the preferred embodiment of the present invention, a kind of magnanimity preparation method of porous oxidation graphene includes the following steps：
1) mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, is original with graphite, mixed acid solution, potassium permanganate
Material prepares graphene oxide, wherein the graphite, mixed acid solution, potassium permanganate mass ratio be 1:182.5:6, it will be made
Graphene oxide be configured to molar concentration be 0.001~20mg/mL graphene oxide water solution；
2) by graphene oxide water solution made from step 1) under the frequency of 15~25KHz ultrasonic disperse 150~
200min obtains finely dispersed graphene oxide water solution；
3) cryogenic liquid is poured slowly into finely dispersed oxidation stone made from step 2) with the rate of 3~1000mL/min
In black aqueous solution, graphene oxide ice cube is obtained；
4) 12~48h of freeze-drying will be carried out at a temperature of -40~-60 DEG C of graphene oxide ice cube that step 3) obtains,
Obtain the porous oxidation graphene.
Compared with prior art, beneficial effects of the present invention are：
(1) the magnanimity preparation method of porous oxidation graphene of the invention, implementation steps are few, without any etching agent to keep away
Exempt to introduce impurity, solvent is not added avoids pyroreaction and solvent volatilizees, by the way that cryogenic liquid is poured slowly into dispersion
Even graphene oxide water solution, porous oxidation graphene can be prepared by being freeze-dried, and simpler in technique, production efficiency is more
Height is lower without special or complex reaction equipment, cost.
(2) the magnanimity preparation method of porous oxidation graphene of the invention, porous oxidation graphene uniform component obtained,
And aperture-controllable, in 1~20 μ m, pore size distribution range is big, is suitable for the magnanimity industrial production of porous oxidation graphene.
(3) the magnanimity preparation method of porous oxidation graphene of the invention, the additive additional without adding etching agent etc.,
Porous oxidation graphene obtained contains-OH ,-COOH, C-O-C ,-C=O etc. compared with polyfunctional group, changes convenient for subsequent functionalization
Property, it can be used for the fields such as electro-catalysis, ultracapacitor, lithium ion battery and organic catalysis.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of graphene oxide prepared by the embodiment of the present invention 1；
Fig. 2 is Fourier Transform Infrared Spectroscopy (FT-IR) figure of graphene oxide prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of porous oxidation graphene prepared by the embodiment of the present invention 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of porous oxidation graphene prepared by the embodiment of the present invention 3；
Fig. 5 is the scanning electron microscope (SEM) photograph of porous oxidation graphene prepared by the embodiment of the present invention 4.
Fig. 6 is the scanning electron microscope (SEM) photograph of porous oxidation graphene prepared by comparative example 1 of the present invention.
Fig. 7 is the scanning electron microscope (SEM) photograph of porous oxidation graphene prepared by comparative example 2 of the present invention.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
The magnanimity preparation method of the porous oxidation graphene of the present invention, includes the following steps：
1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is prepared
Graphene oxide water solution；
2) by graphene oxide water solution ultrasonic disperse made from step 1), it is water-soluble to obtain finely dispersed graphene oxide
Liquid；
3) cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution made from step 2), is aoxidized
Graphene ice cube；
4) the graphene oxide ice cube that step 3) obtains is freeze-dried, obtains the porous oxidation graphene.
Embodiment 1
The preparation of graphene oxide is first by H2SO4And H3PO4It is 9 by volume:1 configuration mixed acid solution.Take 1g scales
Shape graphite is mixed in single-necked flask with 100mL mixed acid solutions, and magnetic agitation makes it be uniformly mixed at room temperature.Mixing will be carried
The single-necked flask of liquid is slowly added to appropriate potassium permanganate as under ice-water bath thereto, and magnetic agitation reacts 1h.Reaction is completed
Single-necked flask is placed in medium temperature thermostat water bath afterwards and stirs certain time.After being cooled to room temperature, then pour them onto containing
In 100mL ice water, hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly.After having reacted, it will react
Sediment freeze-drying is both obtained graphene oxide by product with dilute hydrochloric acid, ethyl alcohol, water centrifuge washing until pH is neutrality respectively.
The transmission electron microscope picture of graphene oxide manufactured in the present embodiment is as shown in Figure 1, it can be seen that obtained oxidation stone
Black alkene is micron-sized large stretch of layered graphite oxide alkene.
Infrared spectrum analysis is carried out to the graphene oxide being prepared, as a result such as the Fourier of the graphene oxide in Fig. 2
Shown in leaf transformation infrared spectrum (FT-IR) figure.As seen from Figure 2,3354cm-1Wider, stronger absorption peak there are one nearby,
This belongs to the stretching vibration peak of O-H；In 1730cm-1Place represents the stretching vibration peak of the C=O on carboxyl；In 1624cm-1
The absorption peak at place is then the bending vibration absorption peak for belonging to C-OH；In 1048cm-1Peak be C-O-C vibration absorption peak；So
Illustrate the groups such as the graphene oxide presence-OH prepared ,-COOH, C-O-C ,-C=O.
Embodiment 2
0.002g graphene oxides are taken, the graphene oxide water solution of a concentration of 1mg/mL of 2mL is configured to, in 20kHz frequencies
Ultrasound 150min, obtains finely dispersed graphene oxide solution under rate.Then by the gaseous liquid nitrogen of room temperature with 30mL/min's
Rate is poured slowly into graphene oxide solution, until solution is frozen into ice cube completely, and it is cold to being carried out at a temperature of its -40 DEG C
Be lyophilized it is dry for 24 hours, you can obtain the graphene oxide with micron hole.The scanning of porous oxidation graphene manufactured in the present embodiment
Electron microscope is as shown in figure 3, as seen from Figure 3, the bore hole size of porous oxidation graphene made from the present embodiment is on 10 μm of left sides
It is right.
Embodiment 3
0.006g graphene oxides are taken, the graphene oxide water solution of a concentration of 3mg/mL of 2mL is configured to, in 18kHz frequencies
Ultrasound 180min, obtains finely dispersed graphene oxide solution under rate.Then by the gaseous liquid nitrogen of room temperature with 50mL/min's
Rate is poured slowly into graphene oxide solution, until solution is frozen into ice cube completely, and it is cold to being carried out at a temperature of its -50 DEG C
Dry 48h is lyophilized, you can obtain the graphene oxide with micron hole.The scanning of porous oxidation graphene manufactured in the present embodiment
Electron microscope is as shown in figure 4, as seen from Figure 4, the bore hole size of porous oxidation graphene is at 4-10 μm made from the present embodiment.
Embodiment 4
0.01g graphene oxides are taken, the graphene oxide water solution of a concentration of 5mg/mL of 2mL is configured to, in 15kHz frequencies
Lower ultrasound 200min, obtains finely dispersed graphene oxide solution.Then liquid nitrogen is poured slowly into the rate of 50mL/min
In graphene oxide solution, until solution is frozen into ice cube completely, and to being freeze-dried at a temperature of its -60 DEG C, you can
Obtain the graphene oxide with micron hole.Scanning electron microscope (SEM) photograph such as Fig. 5 institutes of porous oxidation graphene manufactured in the present embodiment
Show, as seen from Figure 5, the bore hole size of porous oxidation graphene is at 2~5 μm or so made from the present embodiment.
Embodiment 5
0.02g graphene oxides are taken, the graphene oxide water solution of a concentration of 10mg/mL of 2mL is configured to, in 25kHz frequencies
Ultrasound 150min, obtains finely dispersed graphene oxide solution under rate.Then by liquid nitrogen slowly about with the rate of 80mL/min
It pours into graphene oxide solution, until solution is frozen into ice cube completely, and to being freeze-dried at a temperature of its -50 DEG C,
It can be obtained the graphene oxide with micron hole, the bore hole size of porous oxidation graphene is 1~5 made from the present embodiment
μm or so.
Embodiment 6
0.02g graphite oxides are taken, the solution of a concentration of 20mg/mL of 2mL is configured to, the ultrasound 150min under 25kHz frequencies,
Obtain finely dispersed graphene oxide solution.Then liquid nitrogen is about poured slowly into graphene oxide with the rate of 100mL/min
In solution, until solution is frozen into ice cube completely, and to being freeze-dried at a temperature of its -50 DEG C, you can it obtains with micro-
The graphene oxide in metre hole hole, the bore hole size of porous oxidation graphene made from the present embodiment is at 1~5 μm or so.
Comparative example 1
0.02g graphite oxides are taken, the solution of a concentration of 5mg/mL of 2mL is configured to, the ultrasound 150min under 25kHz frequencies,
Obtain finely dispersed graphene oxide solution.Then liquid nitrogen is about quickly poured into graphene oxide solution with 10mL/s rates
In, until solution is frozen into ice cube completely, and to being freeze-dried at a temperature of its -50 DEG C, you can it obtains carrying micron openings
The pore space structure of the graphene oxide in hole, porous oxidation graphene made from this comparative example is imperfect, and lamellar graphite alkene is in liquid nitrogen
It is crushed under gasification impact force and forms fibrous material, scanning electron microscope (SEM) photograph is as shown in Figure 6.
Comparative example 2
0.02g graphite oxides are taken, the solution of a concentration of 5mg/mL of 2mL is configured to, the ultrasound 150min under 25kHz frequencies,
Obtain finely dispersed graphene oxide solution.Then liquid nitrogen is about slowly poured into graphite oxide with 3mL/min rates
In alkene solution, until solution is frozen into ice cube completely, and to being freeze-dried at a temperature of its -50 DEG C, you can it is carried
The graphene oxide of micron hole, the pore space structure of graphene oxide made from this comparative example is apparent, still keeps graphene oxide
Layer structure, scanning electron microscope (SEM) photograph is as shown in Figure 7.
The present invention porous oxidation graphene magnanimity preparation method, implementation steps are few, without any etching agent to avoid
Impurity is introduced, can prepare porous oxidation graphene, simpler, production efficiency higher in technique, without special or complicated anti-
Answer equipment, cost lower；The porous oxidation graphene prepared has the characteristics that large specific surface area, contains compared with polyfunctional group, just
In subsequent functional modification, it can be used for the fields such as electro-catalysis, ultracapacitor, lithium ion battery and organic catalysis.
Above example only is used for illustrating the method detailed of the present invention, and the invention is not limited in above-mentioned method detaileds, i.e.,
Do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode
Deng all falling within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of magnanimity preparation method of porous oxidation graphene, which is characterized in that the magnanimity preparation method includes following step
Suddenly：
1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is matched into oxygenerating
Graphene aqueous solution；
2) by graphene oxide water solution ultrasonic disperse made from step 1), finely dispersed graphene oxide water solution is obtained；
3) cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution made from step 2), obtains graphite oxide
Alkene ice cube；
4) the graphene oxide ice cube that step 3) obtains is freeze-dried, obtains the porous oxidation graphene.
2. magnanimity preparation method according to claim 1, which is characterized in that in step 3), the cryogenic liquid is room temperature
For gaseous cryogenic liquid；
Preferably, the cryogenic liquid is liquid nitrogen or dry ice；
Preferably, the rate that the cryogenic liquid is poured slowly into finely dispersed graphene oxide water solution is 3~100mL/
Min, preferably 40~60mL/min.
3. magnanimity preparation method according to claim 1 or 2, which is characterized in that in step 4), the freeze-drying is true
Vacuum freecing-dry；
Preferably, the temperature of the freeze-drying is -40~-60 DEG C, and the time of the freeze-drying is 12~48h.
4. the magnanimity preparation method according to one of claim 1-3, which is characterized in that in step 1), the Hummers changes
Include the following steps into method：Mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, with graphite, mixed acid solution, Gao Meng
Sour potassium is that raw material prepares graphene oxide.
5. magnanimity preparation method according to claim 4, which is characterized in that the concentrated sulfuric acid and dense phosphorus in the mixed acid solution
The volume ratio of acid is (8~10):1, preferably 9:1；
Preferably, the graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8), preferably 1:
182.5:6。
6. magnanimity preparation method according to claim 4 or 5, which is characterized in that graphene oxide described in step 1)
Preparation process is：
A) by H2SO4And H3PO4It is by volume (8~10):1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation makes it be uniformly mixed at room temperature；It will
Single-necked flask with mixed liquor is slowly added to potassium permanganate as under ice-water bath thereto, and magnetic agitation reacts 1~2h,
The wherein described graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8)；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, then falls reaction solution
In the ice water containing 100mL, hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；It has reacted
Afterwards, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
The graphene oxide.
7. according to claim 1-6 any one of them magnanimity preparation methods, which is characterized in that in step 1), the oxidation stone
The molar concentration of black aqueous solution is 0.001~20mg/mL；
Preferably, the molar concentration of the graphene oxide water solution is 1~10mg/mL.
8. according to claim 1-7 any one of them magnanimity preparation methods, which is characterized in that in step 2), the ultrasound point
Scattered frequency is 15~25KHz, and the time of the ultrasonic disperse is 150~200min.
9. according to claim 1-8 any one of them magnanimity preparation methods, which is characterized in that the porous oxidation graphene
Aperture is 1~20 μm.
10. according to claim 1-9 any one of them magnanimity preparation methods, which is characterized in that the magnanimity preparation method packet
Include following steps：
1) mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, using graphite, mixed acid solution, potassium permanganate as raw material system
Standby graphene oxide, wherein the graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8),
Graphene oxide obtained is configured to the graphene oxide water solution that molar concentration is 0.001~20mg/mL；
2) by graphene oxide water solution made from step 1) under the frequency of 15~25KHz 150~200min of ultrasonic disperse, obtain
To finely dispersed graphene oxide water solution；
3) cryogenic liquid is poured slowly into finely dispersed graphene oxide made from step 2) with the rate of 3~100mL/min
In aqueous solution, graphene oxide ice cube is obtained；
4) 12~48h of freeze-drying will be carried out at a temperature of -40~-60 DEG C of graphene oxide ice cube that step 3) obtains, obtained
The porous oxidation graphene.
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