CN106395808B - A kind of preparation method of graphene oxide - Google Patents
A kind of preparation method of graphene oxide Download PDFInfo
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- CN106395808B CN106395808B CN201610930715.6A CN201610930715A CN106395808B CN 106395808 B CN106395808 B CN 106395808B CN 201610930715 A CN201610930715 A CN 201610930715A CN 106395808 B CN106395808 B CN 106395808B
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- C01B2204/00—Structure or properties of graphene
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
A kind of preparation method of graphene oxide, comprising the following steps: graphite powder is added in the concentrated sulfuric acid under low temperature, is aided with ultrasonic treatment simultaneously under agitation；Sulfuric acid solution is added into resulting mixed solution, and is continually fed into containing ozone gas, is then gradually warming up to medium temperature environment progress constant temperature and is stirred to react；It is continually fed into again containing ozone gas, is then initially added into strong oxidant solution, and be gradually warming up to hot environment progress constant temperature and be stirred to react；After the completion of high-temperature oxydation removing, resulting mixed liquor is subjected to centrifugal treating, isolate supernatant liquor and lower layer's suspension, the dispersion liquid containing graphene oxide is obtained after carrying out Depth Peeling to lower layer's suspension, or obtains graphene oxide powder after carrying out Depth Peeling, centrifuge separation, washing and drying process to lower layer's suspension.It is environmentally protective that the product purity of the method for the present invention preparation is high, safety is good, product lamellar structure spacing is big, spent acid is recycled into use, preparation process.
Description
Technical field
The invention belongs to technical field of new material preparation, and in particular to a kind of preparation method of graphene oxide.
Background technique
Graphene is one layer of two-dimentional carbon material constituted with the periodically closelypacked carbon atom of hexagonal honeycomb structure, is
The density being currently known is minimum, specific surface area is maximum, carrier mobility is maximum, Young's modulus is maximum, translucency is best, conductive
The best material of performance, energy storage field, electronic field, environment protection field, field of compound material, in terms of gather around
There is huge application prospect.But in practical applications, exactly because also these impayable performances, grapheme material are faced with
It is easy to reunite to lead to that bad dispersibility, interface compatibility are poor, are difficult to the puzzlement merged with other materials.
Graphene oxide is as a kind of surface-functionalized Graphene derivative, due to its surface oxygen-containing official rich in
Energy group, on the one hand weakens the interaction force between graphene sheet layer, assigns its excellent dispersion performance；On the other hand it mentions
A large amount of chemical reactivity point has been supplied, good interface is easily compounded to form with other materials.The material can pass through two kinds at present
Means obtain: first is that graphite carries out Depth Peeling through thermal expansion or mechanical means after aoxidizing intercalation processing, obtaining graphite oxide
Alkene, second is that the graphene of the structural integrity obtained using non-oxide reduction is raw material, it is oxidation-treated to obtain graphene oxide, wherein
The former is mainstream preparation process, and specific method mainly has Brodie method, Staudenmaier method, Hummers method and improved
Hummers method.
Brodie method adds KClO in concentrated nitric acid system3For strong oxidizer, when degree of oxidation can be aoxidized by changing
Between controlled, the graphite oxide structure of synthesis is more complete, but needs by repeatedly oxidation, and the reaction time is relatively long,
And more ClO can be generated in the process2Gas；Staudenmaier method is in concentrated nitric acid and concentrated sulfuric acid system with KClO3For oxygen
Agent can generate more Cl in reaction process2And ClO2Equal toxic gases, and it is tighter to graphite oxide structural damage degree
Weight；The advantages that Hummers method is short, degree of oxidation is higher, product structure is more regular, safety coefficient is higher with its oxidization time becomes
Most common preparation method, but this method uses KMnO4As deep oxidation agent, easily leads to wash after product is quenched and be stranded
Difficulty, Mn ion are difficult to cleaning removing and cause product purity not high；In addition, graphene oxide layer structure partly overlaps,
Graphite layers are away from small, it is difficult to which at single layer structure, not washing clean clearly possibly even causes product quality not up to standard, is unable to satisfy for removing
It is required that causing biggish economic loss；Improved Hummers method reduces the use of nitrate, can obtain with high oxidation
The graphite oxide of degree, but this method is complicated still without the introducing and subsequent multiple washing impurity-removing process for avoiding foreign ion,
There are still product quality risks not up to standard.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
It is environmentally protective kind to prepare that product purity is high, safety is good, product lamellar structure spacing is big, spent acid is recycled into use, preparation process
Graphene oxide preparation method.
In order to solve the above technical problems, technical solution proposed by the present invention is a kind of preparation method of graphene oxide, packet
Include following steps:
(1) graphite powder is added in the concentrated sulfuric acid under low temperature, is aided with ultrasonic treatment simultaneously under agitation to carry out
Low temperature intercalation stripping；
(2) after the completion of the low temperature intercalation stripping carried out in above-mentioned steps (1), sulfuric acid is added into resulting mixed solution
Solution, and be continually fed into containing ozone gas as oxidant, it is then gradually warming up to medium temperature environment progress constant temperature and is stirred to react, with
Realize medium temperature oxidation removing；
(3) it after the completion of the medium temperature of above-mentioned steps (2) aoxidizes removing, is continually fed into containing ozone gas as oxidant, so
After be initially added into strong oxidant solution, and be gradually warming up to hot environment carry out constant temperature be stirred to react, with realize high-temperature oxydation shell
From；Being stirred to react in the step (2) and step (3) preferably carries out under ultrasound condition；
(4) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (3), stopping is passed through containing ozone gas, then will be resulting
Mixed liquor carries out centrifugal treating, and isolating supernatant liquor, (volume for the supernatant liquor isolated mixes before being generally centrifugal treating
The 60% ~ 85% of overall solution volume) and lower layer's suspension, it obtains after carrying out Depth Peeling to lower layer's suspension containing graphene oxide
Dispersion liquid, or graphene oxide powder is obtained after carrying out Depth Peeling, centrifuge separation, washing and drying process to lower layer's suspension
Body.
The preparation method of above-mentioned graphene oxide, it is preferred that the graphite powder be natural flake graphite, purity be >=
99%, partial size is 40-1000 mesh.
The preparation method of above-mentioned graphene oxide, it is preferred that the concentrated sulfuric acid under the low temperature is -5 DEG C -5 DEG C 98% dense
Sulfuric acid (unless otherwise instructed, the percentage concentration of sulfuric acid each means mass percent concentration).
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (1), the solid-liquid of graphite powder and the concentrated sulfuric acid
Than controlling the concentrated sulfuric acid for being the g/ml(of 1:10 ~ 80, that is, every gram of graphite powder with addition of 10~80 ml).
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (2), the quality of the sulfuric acid solution is dense
Degree >=70% makes the dosage of graphite powder and the total liquid-solid ratio control of sulfuric acid solution in mixed solution after adding the sulfuric acid solution
System is in the g/ml of 1:30 ~ 100.
The preparation method of above-mentioned graphene oxide, it is preferred that described to contain ozone gas in the step (2) and step (3)
O in body3Concentration >=50%(its can be air-source O3, pure oxygen source O3One or both of combination, ozone is generally O3Occur
Device is made)；The flow control containing ozone gas is 0.1 ~ 10.0 m3/h。
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (2), medium temperature environment refers to 30 DEG C -50 DEG C
Temperature condition.
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (3), hot environment refers to 60 DEG C -80 DEG C
Temperature condition；The time that the constant temperature is stirred to react is at least in 5min or more.
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (3), the strong oxidant solution is matter
Measure the hydrogenperoxide steam generator of score 30%, the additional amount of hydrogenperoxide steam generator according to every gram of graphite powder in mixed solution with addition of 5 ~
The hydrogenperoxide steam generator of 50ml calculates.By in O3Suitable hydrogenperoxide steam generator is added in oxidation process, promotion can be played certainly
The effect of oxidation is generated, further enhanced by base.
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (2), the sulfuric acid solution is derived from step
Suddenly the supernatant liquor isolated in (4) is either originated from the mixed liquor obtained after aforementioned supernatant liquor is mixed with the concentrated sulfuric acid.
The preparation method of above-mentioned graphene oxide, it is preferred that in the step (4), the Depth Peeling is directed to point
Deionized water or dilute acid soln are added in the lower layer's suspension separated out, its deep reaction is made under the conditions of stirring and ultrasonic treatment
5min~300min；The dilute acid soln is resulting after carrying out Depth Peeling, centrifuge separation by the dispersion liquid containing graphene oxide
Supernatant liquor serves as.
The technical solution of aforementioned present invention is based primarily upon following principle:
First is that under cryogenic, the chemical graft of the concentrated sulfuric acid is made full use of to act on to destroy the marginal texture of graphite and invade
Enter inside configuration, while making full use of the mechanical shearing of ultrasonic wave to act on cavitation and destroying interatomic force to increase
Big graphite layers are away from providing advantage for the fully oxidized and splitting of subsequent graphite；
Second is that on the basis of low temperature intercalation stripping tentatively destroys graphite-structure, by the dual mechanical of stirring and ultrasonic wave
The oxidation removing of graphite is strengthened in effect, makes full use of O3The gas fluidity of molecule reinforces the mass transport processes of graphite layers, makes
Free radical come into full contact with graphite carbon atom, play strengthen graphite layers oxidation and increase graphite layers away from it is dual
Purpose；
Third is that making full use of O3Strong oxdiative ability in acid system realizes the deep oxidation of graphite, on the one hand utilizes
O3Direct oxidation act on to destroy the carbon-carbon double bond in benzene ring structure, for free radical combination provide activate site；Another party
Face O3The very high free radical of oxidation activity can be generated in decomposable process, make full use of the chemical activity of the free radical, make its with
While graphite carbon atom is combined and is oxidized, part free radical, which further generates oxidation, to be made to be grafted to graphite layer surface
Sulfonic acid group decompose, play the role of enhancing oxidation and removal of impurities.
Fourth is that making full use of mechanical stirring to be superimposed with ultrasonic wave in graphite oxidation stripping process and using generated machinery
Shearing effect, cavitation effect, chemical strengthening effect and fuel factor effect, the oxidation on the one hand strengthening graphite layers carbon atom are anti-
It answers, chemically reacts angle and widen graphite layers away from another aspect destroys interatomic force and accelerates to remove fragment in solution
In movement, from mechanical angle realize graphite Depth Peeling with it is evenly dispersed.
Fifth is that after graphite oxidation stripping reaction finishes, continue with produced by mechanical stirring is superimposed use with ultrasonic wave
Mechanical shearing effect, cavitation effect and fuel factor effect carry out Depth Peeling, further destroy interatomic force to obtain
Smaller, thinner single-layer graphene film, while accelerating the movement of graphite scrap in the medium, it prevents from reuniting, to obtain
Obtain evenly dispersed graphene dispersing solution.
Compared with prior art, the innovation of the invention consists in that:
1, the KMnO that the present invention uses the graphite oxidation stage in traditional reaction process4Oxidant replaces with ozone (O3) strong
On the one hand oxidant makes full use of the flowability of strong oxidizing property gas to strengthen mass transport process, the intercalation of graphite is accelerated to aoxidize
Reaction is conducive to increase interlamellar spacing；On the other hand the introducing of foreign ion can be greatly decreased, overcome in conventional preparation techniques and exist
Metal ion difficulty cleaning the problem of, the purity is high of products obtained therefrom；
2, the present invention gives full play to the superposition cumulative effect of chemical action and mechanism, strengthens graphite by mechanism
The chemical oxidation of carbon atom acts on, and acceleration mechanical shearing removing and dispersion mass transfer, the two are mutually auxiliary on the basis of chemical oxidation
Coordinate, promote mutually, realize the Depth Peeling of graphite with it is evenly dispersed, in products obtained therefrom 1-2 layers of graphene yield be up to 50% with
On；
3, the present invention realizes the circulating and recovering step by step of each stage acid solution, and no waste acid liquor outlet is substantially evaded
The discharge of spent acid present in prior art and processing problem, significantly reduce the environmental of the preparation process, simultaneously also
The circulating and recovering for realizing sulfuric acid resource reduces the economic cost and environmentally friendly cost of the preparation process.Specific manifestation are as follows: (1)
The present invention is isolated most sulfuric acid solution by the way of centrifugation, added thereto suitable after the oxidation for completing graphite
It is recycled into after the amount concentrated sulfuric acid and uses graphite medium temperature oxidation stripping bench；(2) after completing graphite Depth Peeling, using centrifugation
The upper layer dilute acid soln that mode is isolated, can direct reuse to the graphite Depth Peeling stage；
4, due to not introducing other impurities ion in this process, the sulfonic acid group being grafted in intercalation oxidation process can be in the later period
The further oxydrolysis removing of high-temperature oxydation stripping bench, products obtained therefrom purity is high, without repeatedly washing, to can reach purity big
In 99.9% graphene oxide product, avoid repeatedly washed in conventional preparation techniques be also difficult to realize impurity deep removal
Problem.
Generally speaking, the present invention provides an efficient stable, the preparation process route of environmentally protective graphene oxide,
The deficiencies of activation of graphene existing for traditional acid oxidation is difficult to control, product purity is not high is overcome, the product being prepared is pure
Degree is high, and (chemical purity >=99.9% of graphene oxide powder, specific surface area are 600 ~ 1500m2/ g, 1-2 layers of graphene oxide produce
Rate >=50%), safety is good, product lamellar structure spacing is big, preparation process is environmentally protective.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the process flow chart of the preparation method of graphene oxide of the invention.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of graphene oxide of the invention as shown in Figure 1, specifically includes the following steps:
(1) concentrated sulfuric acid of 50ml 98% is measured in three-necked flask, is subsequently placed in ice-water bath and is cooled to 0 DEG C；
(2) ultrasonication is opened, the 2g graphite powder (natural flake graphite from Chenzhou, Hunan Province graphite factory is accurately weighed
Sample, its chemical purity is 99.9% after ore dressing removal of impurities processing, and granularity is 40 mesh ~ 400 mesh), by stone while ultrasonication
Ink powder is slowly added in three-necked flask, is aided with ultrasonic treatment simultaneously under agitation, reacts 60min to carry out low temperature intercalation stripping
From；
(3) after the completion of the low temperature intercalation stripping carried out in the above-mentioned steps (2), continual ultrasonic processing and stir it is constant, to
80% sulfuric acid solution of 50ml is added in resulting mixed solution, and continues to be passed through the pure oxygen source that purity is 90% into three-necked flask
O3Gas is as oxidant, gas flow rate 2m3/ h, then slow heating water bath makes it gradually be warming up to 40 DEG C of environment progress permanent
Temperature is stirred to react 60min, to realize medium temperature oxidation removing；
(4) after the completion of the medium temperature of above-mentioned steps (3) aoxidizes removing, it is continually fed into above-mentioned pure oxygen source O3Gas is as oxidation
Then agent starts the hydrogenperoxide steam generator that 30ml 30% is added to three-necked flask, heating water bath is warming up to 70 DEG C of high temperature rings again
Border carries out constant temperature and is stirred to react 90min, to realize that high-temperature oxydation is removed；
(5) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (4), stopping is passed through containing ozone gas, then will be resulting
Mixed liquor carries out centrifugal treating, isolates supernatant liquor (90ml) and lower layer's suspension, and it is appropriate dense to isolate supernatant liquor supplement
The graphite medium temperature oxidation stripping bench that above-mentioned steps (3) are back to use after sulfuric acid is filled into as sulfuric acid solution, is then taken under 45ml
200ml deionized water is added in beaker in layer suspension thereto, and continual ultrasonic and stir process make its deep reaction 60min,
Stirring and ultrasonic wave are closed, the graphene oxide dispersion of glassy yellow is obtained；
(6) the resulting graphene oxide dispersion of step (5) is subjected to centrifugal treating, obtained 220ml supernatant liquor can
Being back to use in above-mentioned steps (5) replaces the deionized water being added to carry out the Depth Peeling of graphite, and obtained lower sediment adds
It after ion water washing to neutrality, filtered, be dried in vacuo up to graphene oxide powder.
Through being analyzed and characterized, the chemical purity of the resulting graphene oxide powder product of the present embodiment is 99.95%, 1-2 layers of oxygen
The yield of graphite alkene is 68%, and the specific surface area of product is 924m2/g。
Embodiment 2:
A kind of preparation method of graphene oxide of the invention as shown in Figure 1, specifically includes the following steps:
(1) concentrated sulfuric acid of 80ml 98% is measured in three-necked flask, is subsequently placed in ice-water bath and is cooled to -2 DEG C；
(2) ultrasonication is opened, the 4g graphite powder (natural flake graphite from Chenzhou, Hunan Province graphite factory is accurately weighed
Sample, its chemical purity is 99.92% after ore dressing removal of impurities processing, and granularity is 200 mesh ~ 1000 mesh), while ultrasonication
Graphite powder is slowly added in above-mentioned three-necked flask, is aided with ultrasonic treatment simultaneously under agitation, reaction 30min is low to carry out
Warm intercalation stripping；
(3) after the completion of the low temperature intercalation stripping carried out in the above-mentioned steps (2), continual ultrasonic processing and stir it is constant, to
75% sulfuric acid solution of 70ml is added in resulting mixed solution, and continues to be passed through the air-source that purity is 60% into three-necked flask
O3Gas is as oxidant, gas flow rate 5m3/ h, then slow heating water bath make its be gradually warming up to 40 DEG C of medium temperature environment into
Row constant temperature is stirred to react 100min, to realize medium temperature oxidation removing；
(4) after the completion of the medium temperature of above-mentioned steps (3) aoxidizes removing, it is continually fed into above-mentioned air-source O3Gas is as oxidation
Then agent starts the hydrogenperoxide steam generator that 50ml 30% is added to three-necked flask, heating water bath is warming up to 80 DEG C of high temperature rings again
Border carries out constant temperature and is stirred to react 60min, to realize that high-temperature oxydation is removed；
(5) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (4), stopping is passed through containing ozone gas, then will be resulting
Mixed liquor carries out centrifugal treating, isolates supernatant liquor (150ml) and lower layer's suspension, and it is appropriate dense to isolate supernatant liquor supplement
The graphite medium temperature oxidation stripping bench that above-mentioned steps (3) are back to use after sulfuric acid is filled into as sulfuric acid solution, is then taken under 60ml
In beaker 300ml deionized water is added, continual ultrasonic and stir process make its deep reaction in layer suspension thereto
100min closes stirring and ultrasonic wave, obtains the graphene oxide dispersion of glassy yellow；
(6) the resulting graphene oxide dispersion of step (5) is subjected to centrifugal treating, obtained 320ml supernatant liquor can
Being back to use in above-mentioned steps (5) replaces the deionized water being added to carry out the Depth Peeling of graphite, and obtained lower sediment adds
It after ion water washing to neutrality, filtered, be dried in vacuo up to graphene oxide powder.
Through being analyzed and characterized, the chemical purity of the resulting graphene oxide powder product of the present embodiment is 99.98%, 1-2 layers of oxygen
The yield of graphite alkene is 71%, and the specific surface area of product is 1258m2/g。
Embodiment 3:
A kind of preparation method of graphene oxide of the invention as shown in Figure 1, specifically includes the following steps:
(1) concentrated sulfuric acid of 100ml 98% is measured in three-necked flask, is subsequently placed in ice-water bath and is cooled to 2 DEG C；
(2) ultrasonication is opened, 5g graphite powder (the natural scale stone from Changsha Graphite Company is accurately weighed
Black sample, its chemical purity is 99.9% after ore dressing removal of impurities processing, and granularity is 200 mesh ~ 600 mesh), while ultrasonication
Graphite powder is slowly added in above-mentioned three-necked flask, is aided with ultrasonic treatment simultaneously under agitation, reaction 60min is low to carry out
Warm intercalation stripping；
(3) after the completion of the low temperature intercalation stripping carried out in the above-mentioned steps (2), continual ultrasonic processing and stir it is constant, to
80% sulfuric acid solution of 100ml is added in resulting mixed solution, and continues to be passed through the pure oxygen source that purity is 70% into three-necked flask
With air-source O3Mixed gas is as oxidant, gas flow rate 6m3/ h, then slow heating water bath makes it gradually be warming up to 45
DEG C medium temperature environment carries out constant temperature and is stirred to react 100min, to realize medium temperature oxidation removing；
(4) after the completion of the medium temperature of above-mentioned steps (3) aoxidizes removing, above-mentioned pure oxygen source and air-source O are continually fed into3Mixing
Then gas starts the hydrogenperoxide steam generator that 50ml 30% is added to three-necked flask, heating water bath heats up again as oxidant
Constant temperature is carried out to 80 DEG C of hot environments and is stirred to react 120min, to realize that high-temperature oxydation is removed；
(5) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (4), stopping is passed through containing ozone gas, then will be resulting
Mixed liquor carries out centrifugal treating, isolates supernatant liquor (180ml) and lower layer's suspension, and it is appropriate dense to isolate supernatant liquor supplement
The graphite medium temperature oxidation stripping bench that above-mentioned steps (3) are back to use after sulfuric acid is filled into as sulfuric acid solution, is then taken under 80ml
In beaker 320ml deionized water is added, continual ultrasonic and stir process make its deep reaction in layer suspension thereto
150min closes stirring and ultrasonic wave, obtains the graphene oxide dispersion of glassy yellow；
(6) the resulting graphene oxide dispersion of step (5) is subjected to centrifugal treating, obtained 350ml supernatant liquor can
Being back to use in above-mentioned steps (5) replaces the deionized water being added to carry out the Depth Peeling of graphite, and obtained lower sediment adds
It after ion water washing to neutrality, filtered, be dried in vacuo up to graphene oxide powder.
Through being analyzed and characterized, the chemical purity of the resulting graphene oxide powder product of the present embodiment is 99.96%, 1-2 layers of oxygen
The yield of graphite alkene is 54%, and the specific surface area of product is 695m2/g。
Embodiment 4:
A kind of preparation method of graphene oxide of the invention as shown in Figure 1, specifically includes the following steps:
(1) concentrated sulfuric acid of 80ml 98% is measured in three-necked flask, is subsequently placed in ice-water bath and is cooled to 0 DEG C；
(2) ultrasonication is opened, 5g graphite powder (the natural scale stone from Changsha Graphite Company is accurately weighed
Black sample, its chemical purity is 99.9% after ore dressing removal of impurities processing, and granularity is 200 mesh ~ 600 mesh), while ultrasonication
Graphite powder is slowly added in above-mentioned three-necked flask, is aided with ultrasonic treatment simultaneously under agitation, reaction 60min carries out low temperature
Intercalation stripping；
(3) after the completion of the low temperature intercalation stripping carried out in the above-mentioned steps (2), continual ultrasonic processing and stir it is constant, to
71% sulfuric acid solution of 200ml is added in resulting mixed solution, and (sulfuric acid solution is by centrifugation in 3 step of above-described embodiment (5)
The 180ml supernatant liquor and 98% concentrated sulfuric acid mixed preparing of 20ml isolated form), and continue to be passed through purity into three-necked flask
For 60% air-source O3Mixed gas is as oxidant, gas flow rate 5m3/ h, then slow heating water bath makes it gradually heat up
Constant temperature is carried out to 45 DEG C of medium temperature environment and is stirred to react 150min, to realize medium temperature oxidation removing；
(4) after the completion of the medium temperature of above-mentioned steps (3) aoxidizes removing, it is continually fed into above-mentioned air-source O3Mixed gas conduct
Then oxidant starts the hydrogenperoxide steam generator that 50ml 30% is added to three-necked flask, heating water bath is warming up to 70 DEG C of height again
Warm environment carries out constant temperature and is stirred to react 150min, to realize that high-temperature oxydation is removed；
(5) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (4), stopping is passed through containing ozone gas, then will be resulting
Mixed liquor carries out centrifugal treating, isolates supernatant liquor (250ml) and lower layer's suspension, and it is appropriate dense to isolate supernatant liquor supplement
The graphite medium temperature oxidation stripping bench that above-mentioned steps (3) can be back to use after sulfuric acid is filled into as sulfuric acid solution, then takes 90ml
Lower layer's suspension is in beaker, and 350ml dilute acid soln is added thereto, and (dilute acid soln is 3 step of above-described embodiment (6) separation
Supernatant liquor out, wherein H2SO4Concentration is that 14.5%), continual ultrasonic and stir process make its deep reaction 240min, is closed
Stirring and ultrasonic wave, obtain the graphene oxide dispersion of glassy yellow；
(6) the resulting graphene oxide dispersion of step (5) is subjected to centrifugal treating, obtained 380ml supernatant liquor can
Being back to use in above-mentioned steps (5) replaces the dilute acid soln being added to carry out the Depth Peeling of graphite, and obtained lower sediment adds
It after ion water washing to neutrality, filtered, be dried in vacuo up to graphene oxide powder.
Through being analyzed and characterized, the chemical purity of the resulting graphene oxide powder product of the present embodiment is 99.96%, 1-2 layers of oxygen
The yield of graphite alkene is 51%, and the specific surface area of product is 704m2/g。
Claims (6)
1. a kind of preparation method of graphene oxide, which comprises the following steps:
(1) graphite powder is added in the concentrated sulfuric acid under low temperature, is aided with ultrasonic treatment simultaneously under agitation to carry out low temperature
Intercalation stripping；
(2) after the completion of the low temperature intercalation stripping carried out in above-mentioned steps (1), it is molten that sulfuric acid is added into resulting mixed solution
Liquid, and be continually fed into containing ozone gas as oxidant, it is then gradually warming up to medium temperature environment progress constant temperature and is stirred to react, with reality
Existing medium temperature oxidation removing；
(3) it after the completion of the medium temperature of above-mentioned steps (2) aoxidizes removing, is continually fed into containing ozone gas as oxidant, then opens
Begin that strong oxidant solution is added, and be gradually warming up to hot environment progress constant temperature and be stirred to react, to realize that high-temperature oxydation is removed；
(4) after the completion of the removing of the high-temperature oxydation of above-mentioned steps (3), stopping is passed through containing ozone gas, then by resulting mixing
Liquid carries out centrifugal treating, isolates supernatant liquor and lower layer's suspension, oxygen-containing to obtaining after lower layer's suspension progress Depth Peeling
The dispersion liquid of graphite alkene, or oxygen is obtained after carrying out Depth Peeling, centrifuge separation, washing and drying process to lower layer's suspension
Graphite alkene powder；
In the step (2), mass concentration >=70% of the sulfuric acid solution makes to mix after adding the sulfuric acid solution
The dosage of graphite powder is controlled with the total liquid-solid ratio of sulfuric acid solution in 1:30~100g/ml in solution；
It is described containing O in ozone gas in the step (2) and step (3)3Concentration >=50%；The flow velocity control containing ozone gas
It is made as 0.1~10.0m3/h；
In the step (3), the strong oxidant solution is the hydrogenperoxide steam generator of mass fraction 30%, hydrogenperoxide steam generator
Hydrogenperoxide steam generator of the additional amount according to every gram of graphite powder in mixed solution with addition of 5~50ml calculates；
In the step (1), low temperature refers to -5 DEG C -5 DEG C；In the step (2), medium temperature environment refers to 30 DEG C of -50 DEG C of temperature strips
Part；In the step (3), hot environment refers to 60 DEG C of -80 DEG C of temperature conditions；The time that the constant temperature is stirred to react at least exists
5min or more.
2. the preparation method of graphene oxide according to claim 1, which is characterized in that the graphite powder is natural scale
Graphite, purity are >=99%, and partial size is 40-1000 mesh；The concentrated sulfuric acid is 98% concentrated sulfuric acid.
3. the preparation method of graphene oxide according to claim 1, which is characterized in that in the step (1), graphite powder
Solid-to-liquid ratio control with the concentrated sulfuric acid is 1:10~80g/ml.
4. the preparation method of graphene oxide according to any one of claim 1-3, which is characterized in that the step
(2) in, the sulfuric acid solution is derived from the supernatant liquor isolated in step (4) or is originated from aforementioned supernatant liquor and dense sulphur
The mixed liquor that acid-mixed obtains after closing.
5. the preparation method of graphene oxide according to any one of claim 1-3, which is characterized in that the step
(4) in, the Depth Peeling is directed to that deionized water or dilute acid soln are added in the lower layer's suspension isolated, and is stirring and is surpassing
Make its deep reaction 5min~300min under the conditions of sonication；The dilute acid soln is carried out by the dispersion liquid containing graphene oxide
Resulting supernatant liquor serves as after Depth Peeling, centrifuge separation.
6. the preparation method of graphene oxide according to any one of claim 1-3, which is characterized in that the step
(2) being stirred to react and in step (3) is carried out under ultrasound condition.
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| CN107195879A (en) * | 2017-05-09 | 2017-09-22 | 东南大学 | A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery |
| CN107226469A (en) * | 2017-08-03 | 2017-10-03 | 山东金城石墨烯科技有限公司 | A kind of method that one-step method prepares graphene oxide |
| CN107857260B (en) * | 2017-12-13 | 2020-02-07 | 西北有色金属研究院 | Method for preparing graphene oxide through weak oxidation intercalation stripping |
| CN110184671A (en) * | 2018-04-12 | 2019-08-30 | 济南开发区星火科学技术研究院 | A kind of graphene composite fibre |
| CN109181374A (en) * | 2018-08-23 | 2019-01-11 | 广东思泉新材料股份有限公司 | A method of it prepares with high-heating radiation graphene coating |
| CN111410855A (en) * | 2019-12-31 | 2020-07-14 | 宁波德泰化学有限公司 | Preparation method of high-surface-activity/high-hydrophilicity dispersion type carbon black |
| CN112174134A (en) * | 2020-11-12 | 2021-01-05 | 常州第六元素材料科技股份有限公司 | Method for preparing graphite oxide by circulating sulfuric acid |
| CN115448304A (en) * | 2022-10-12 | 2022-12-09 | 齐鲁工业大学 | Method for preparing graphene oxide in high-safety efficient water bath |
| CN115893396A (en) * | 2022-10-25 | 2023-04-04 | 哈尔滨工业大学 | Preparation method of cassava residue derived graphene oxide film |
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| CN103145121B (en) * | 2013-03-19 | 2015-04-29 | 苏州格瑞丰纳米科技有限公司 | Preparation method of thin-layer graphene oxide material |
| CN105129790A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Novel method for preparing graphene oxide under supercritical water condition |
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| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN105129790A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Novel method for preparing graphene oxide under supercritical water condition |
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