CN102557018A - Preparation method of graphene based on green deoxidation technology - Google Patents
Preparation method of graphene based on green deoxidation technology Download PDFInfo
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Abstract
The invention discloses a preparation method of graphene based on a green deoxidation technology, which comprises the following steps: preparing graphene oxide through the intercalated oxidation of graphite; and finishing the conversion from the graphene oxide to the graphene through a green deoxidizer. The preparation method has the beneficial effects that the graphene can be quickly prepared in batch through heating the adopted green deoxidizer, the deoxidizer can be recycled, and the reaction tail gas is single and is convenient to collect so as to achieve the green low-carbon production purpose. A deoxidizing section has the advantages of simplicity and convenience in operation, safety, low cost and zero emission.
Description
[technical field]
The present invention relates to the two-dimensional nano preparation methods, particularly a kind of method based on green deoxy technology batch preparations single-layer graphene.
[background technology]
Graphene is a kind of by the tightly packed two dimensional crystal that constitutes of carbon atom, is the essentially consist unit of allotropic substance that comprises the carbon of soccerballene, carbon nanotube, graphite.Graphene has characteristics such as special optics, electricity, calorifics, mechanics, and it has second integer quantum hall effect of room temperature, and quantum is worn effect then, high speed electronic mobility 20000m
2V
-1s
-1, high heat conductance 3000Wm
-1K
-1With outstanding mechanical property (high-modulus 1060GPa, HS 130GPa).Can not only make nanoelectronics and the spintronics components and parts of respectively providing the ability that has specific characteristics with these characteristic Graphenes; And utilize its two dimensional structure; Can use the semiconductor light carving technology of standard to carry out the design of extensive integrated nano-electron circuit, make aspects such as functional composite material, energy storage material, support of the catalyst and have wide practical use.But the commercial application of Graphene is to be based upon on the basis of its scale operation.Therefore a large amount of scientist are placed on research emphasis on the suitability for industrialized production of Graphene both at home and abroad.Graphene is successfully made by the method that Britain physicist An Deliehaimu and Constantine Nuo Woxiaoluofu peel off through micromechanics the earliest, and the maximum shortcoming of this method is to yield poorly.Preparation method of graphene can be divided into 4 big types up till now: micromechanics is peeled off method, chemical Vapor deposition process, epitaxial growth method, preparation soliquid method.But because the hydrophobicity of Graphene self, and the character of the reunion in solvent has all produced restriction to its preparation.From with short production cycle, and the high angle of output sets out in performance obtained in laboratory research, thinks that in the world wet-chemical oxidation-reduction method in the preparation soliquid method has the potentiality of scale operation.
The wet-chemical oxidation-reduction method is meant and earlier the graphite raw material oxidation is obtained graphite oxide, makes graphene oxide through peeling off, the method that restores.Method for oxidation commonly used has only three kinds: Brodie; Staudenmaier or Hummers; Method of reducing is then studied more; Method of reducing commonly used has that chemical liquid phase reduction, plasma method reduction, thermal reduction, hydrogen arc-over are peeled off, photoreduction, microwave reduction etc., and what use always is chemical reduction, Hydrazine Hydrate 80, H
2, NaBH
4, vitamins C, quadrol, Na/CH
3OH etc.But these methods can in the face of the reductive agent high toxicity and can not recycle, reaction time length, high energy consumption, the direct discharging of tail gas problem such as can't handle, thereby suitability for industrialized production is brought obstruction.
[summary of the invention]
To the deficiency of existing graphene preparation method, the object of the present invention is to provide a kind of preparation method of graphene based on green deoxy technology that can solve following technical problem:
1, through the selecting for use of reductor, as select yellow soda ash for use, salt of wormwood etc. are realized reductor cyclic production, nontoxic, the deoxidation process of the graphene oxide of zero release;
2, reduce the reaction times of deoxidation process;
3, through introducing the weakly alkaline of carbonate, improve the stability of Graphene at aqueous phase system.
In order to realize above-mentioned goal of the invention, the present invention adopts following technical scheme:
1, the intercalation oxidation of graphite;
2, peeling off of graphite oxide obtains graphene oxide;
3, make graphene oxide transform through reductor to Graphene;
4, the tail gas of green deoxidation process generation is pure carbon dioxide, can directly recycle, and realizes zero carbon emission.
Specific embodiments of the present invention is following:
1, the intercalation oxidation of graphite
(1), press the proportioning of graphite and preoxidation agent, put into flask; Press the proportioning of graphite and intercalation oxygenant, the intercalation oxygenant is slowly added, temperature control is to suitable temperature, and magnetic agitation makes uniform and stable the reacting of reaction system.
(2), the proportioning of pressing graphite and strong oxidizer, the strong oxidizer gradation slowly is added in the reactions step (1); The rapid constant temperature of the temperature of reaction system is to suitable temperature, and magnetic agitation is reacted to the suitable time.
(3), after reactions step (2) finishes, add proper amount of deionized water reaction system carried out reaction terminating, regulate temperature of reaction under the magnetic agitation to suitable value, heat tracing, magnetic agitation.
(4), question response step (3) reaction system steadily after, the proportioning of press graphite and strong oxidizer, adding strong oxidizer, and use a certain amount of deionized water that reaction system is carried out secondary dilution obtains suspension-s. heat tracing, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
2, peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained disperses in an amount of water, and through suitable power, the regular hour is carried out ultra-sonic dispersion, makes the suspension-s of graphene oxide in water under the finite concentration.
3, through reductor graphene oxide is transformed to Graphene
(1), in the suspension-s that reactions step 2 makes, by the aqueous solution of certain density green reductor and the proportioning of graphene oxide, add the aqueous solution of green reductor; Magnetic agitation mixes, under suitable temperature, and insulation reaction; Deoxidation finishes behind the certain hour, obtains reaction liquid; Reaction system sealing,, and the carbonic acid gas that produces collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is placed in the round-bottomed flask; Add zeolite and under suitable temperature, carry out underpressure distillation; Be concentrated to the required concentration of reactions step 3; The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because reaction system can not polluted green reductor, so can recycle green reductor for a long time.
Preparation method of graphene of the present invention, as graphite, optional natural graphite, synthetic graphite, expanded graphite, the loose oxidation of intercalation or natural graphite of peeling off and the expanded graphite be convenient to of preferred laminated structure; As the intercalation oxygenant, the optional vitriol oil, phosphoric acid, preferred 98% vitriol oil; As the preoxidation agent, optional SODIUMNITRATE, saltpetre, preferred SODIUMNITRATE; As strong oxidizer, optional potassium permanganate, oxygen acid potassium, SODIUMNITRATE, ydrogen peroxide 50, preferred potassium permanganate or ydrogen peroxide 50; As green reductor, optional carbonate material, one or more in preferred yellow soda ash, salt of wormwood, the Quilonum Retard.
The aqueous solution of the described graphite of such scheme and preoxidation agent, graphite and strong oxidizer, graphite and intercalation oxygenant and green reductor and water, green reductor and the proportioning of graphene oxide (in dry weight part, down together) are:
The proportioning of graphite and intercalation oxygenant 1: 10～1: 100, preferred 1: 30～1: 60; The proportioning of graphite and preoxidation agent 1: 0～1: 2, preferred 1: 0.2～1: 1; The proportioning of graphite and strong oxidizer 1: 2～1: 7, preferred 1: 3～1: 6; The proportioning of green reductor and water 0.005: 1～3.2: 1, preferred 0.05: 1～3.2: 1; The aqueous solution of green reductor and the proportioning of graphene oxide 1: 200～100: 2, preferred 1: 100～100: 1.
Therefore, a kind of preparation method of graphene based on green deoxy technology of the present invention, preferably adopt following embodiment:
1, the intercalation oxidation of graphite
(1), presses natural graphite or expanded graphite: the proportioning of SODIUMNITRATE 1: 0.2～1: 1; Take by weighing natural graphite or expanded graphite and SODIUMNITRATE, and feed intake in flask, press natural graphite or expanded graphite: the proportioning of 98% vitriol oil 1: 30～1: 60; Slowly add 98% vitriol oil; Temperature of reaction is controlled at 0～5 ℃, and magnetic agitation makes reaction system uniform and stable.
(2), after question response step (1) carries out 10min～2h, press natural graphite or expanded graphite: the proportioning of potassium permanganate 1: 3～1: 6, gradation slowly adds potassium permanganate; Magnetic agitation, temperature of reaction are controlled at 25～45 ℃
(3), after reactions step (2) is carried out 2h～36h, add deionized water 100～300mL, termination reaction is regulated temperature of reaction to 40～120 ℃ under the magnetic agitation.
(4), question response step (3) carries out 10mim～2h, reaction system steadily after, add ydrogen peroxide 50 10～50mL, remove the Manganse Dioxide of generation, and use the deionized water of 120-280mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
Peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 50～500W, ultrasonic 2～30min makes the suspension-s of graphene oxide in water.
3, make graphene oxide transform through reductor to Graphene
(1), in the suspension-s that reactions step 2 makes, press the volume ratio 1: 100～100: 1 of the graphene oxide aqueous solution and the green reductor aqueous solution (proportioning of green reductor and water 0.05: 1～3.2: 1), add one or more the aqueous solution in green reductor yellow soda ash, salt of wormwood, the Quilonum Retard; Be heated to 50～120 ℃, magnetic agitation mixes; Reaction times 3min～5h; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is placed in the round-bottomed flask, adds zeolite and under 40～130 ℃, carries out underpressure distillation, is concentrated to the required concentration of reactions step 3; The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because reaction system can not polluted green reductor, so can recycle green reductor for a long time.
[key problem in technology point of the present invention]
Key problem in technology point of the present invention is:
Adopted carbonate as green reductor, and carbonate and deionized water have been processed the solution of stable homogeneous.Because the carbonate in the carbonate aqueous solution can be emitted a certain amount of oxonium ion, thereby the carbon that links to each other with oxy radical on the graphene oxide is carried out the purpose that attack reaches deoxidation.It is very fast that the reaction of carbonic acid gas is taken off in the oxonium ion attack, mild condition, thus make reaction be convenient to control, the reaction times is short; The product that the system deoxidation produces is a carbonic acid gas, also is unique side product, is convenient to collection, thereby reaches the working method of the green low-carbon of zero release; The dispersion that Graphene can be stable under alkaline condition.
[effect of the present invention]
The green reductor that the present invention adopts is under aqueous conditions; Just can be quick through heated and stirred under the lesser temps, passing through in batches advances deoxidation to graphene oxide and prepares Graphene, and green reductor itself can be recycled through underpressure distillation under the lesser temps; The tail gas of deoxidation process generation simultaneously is single; Consist of carbonic acid gas, be convenient to collection, thereby reach the production purpose of green low-carbon; Deoxidation section of the present invention is easy and simple to handle, and safety is with low cost, zero release, and green reductor can recycle, and the Graphene product aqueous phase dispersibility of preparation is good, is difficult for reuniting, and carbon-carbon double bond keeps more, possesses high conduction potentiality.
[specific embodiments]
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within institute of the present invention restricted portion equally.Ratio range among the embodiment is the ratio of dry weight.
Embodiment one
Based on green deoxy technology graphene preparation method, comprise following reactions step:
1, the intercalation oxidation of graphite
(1), take by weighing natural graphite 4g, SODIUMNITRATE 3g drops in the flask, slowly adds 98% vitriol oil 120mL, uses the thermostat water bath temperature control at 0 ℃, magnetic agitation makes uniform and stable the carrying out of reaction system.
(2), after question response step (1) carries out 1h, gradation slowly adds potassium permanganate 20g, magnetic agitation, temperature of reaction are controlled at 30 ℃.
(3), after reactions step (2) is carried out 24h, add deionized water 100mL, reaction system is carried out termination reaction, regulate temperature of reaction to 75 ℃ under the magnetic agitation.
(4), the question response step enters (3) and carries out 20mim, reaction system steadily after, add ydrogen peroxide 50 35mL, remove the Manganse Dioxide of generation, and use the deionized water of 150mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite
Peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 200W, ultrasonic 10min, making concentration is the suspension-s of graphene oxide in water of 2mg/mL.
3, through reductor graphene oxide is transformed to Graphene
(1), green reductor salt of wormwood 100g of adding and 100g water mix in the suspension-s that reactions step 2 makes; The graphene oxide aqueous solution mixed with the green reductor aqueous solution in 1: 1 by volume, heated 70 ℃, and magnetic agitation mixes; Reaction times 5min; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene 2.5g and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is carried out underpressure distillation and is concentrated to the required concentration of reactions step 3,60 ℃ of distillation temperatures.The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because can not be contaminated, so can recycle green reductor for a long time.
Embodiment two
Based on green deoxy technology graphene preparation method, comprise following reactions step:
1, the intercalation oxidation of graphite
(1), take by weighing expanded graphite 4g, SODIUMNITRATE 2g drops in the flask, slowly adds 98% vitriol oil 160mL, uses the thermostat water bath temperature control at 3 ℃, magnetic agitation makes uniform and stable the carrying out of reaction system.
(2), after question response step (1) carries out 30min, gradation slowly adds potassium permanganate 22g, magnetic agitation, temperature of reaction are controlled at 26 ℃.
(3), after reactions step (2) is carried out 5h, add deionized water 200mL, reaction system is carried out termination reaction, regulate temperature of reaction to 45 ℃ under the magnetic agitation.
(4), the question response step enters (3) and carries out 1h, reaction system steadily after, add ydrogen peroxide 50 15mL, remove the Manganse Dioxide of generation, and use the deionized water of 150mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
2, peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 60W, ultrasonic 30min, making concentration is the suspension-s of graphene oxide in water of 2mg/mL.
3, through reductor graphene oxide is transformed to Graphene
(1), green reductor yellow soda ash 150g of adding and 100g water mix in the suspension-s that reactions step 2 makes; The graphene oxide aqueous solution mixed with the green reductor aqueous solution in 10: 1 by volume, heated 55 ℃, and magnetic agitation mixes; Reaction times 5h; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene 2.7g and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is carried out underpressure distillation and is concentrated to the required concentration of reactions step 3,70 ℃ of distillation temperatures.The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because can not be contaminated, so can recycle green reductor for a long time.
Embodiment three
Based on green deoxy technology graphene preparation method, comprise following reactions step:
1, the intercalation oxidation of graphite
(1), take by weighing expanded graphite 4g, SODIUMNITRATE 1g drops in the flask, slowly adds 98% vitriol oil 200mL, uses the thermostat water bath temperature control at 5 ℃, magnetic agitation makes uniform and stable the carrying out of reaction system.
(2), after question response step (1) carries out 2h, gradation slowly adds potassium permanganate 17g, magnetic agitation, temperature of reaction are controlled at 35 ℃.
(3), after reactions step (2) is carried out 7h, add deionized water 300mL, reaction system is carried out termination reaction, regulate temperature of reaction to 90 ℃ under the magnetic agitation.
(4), the question response step enters (3) and carries out 2h, reaction system steadily after, add ydrogen peroxide 50 35mL, remove the Manganse Dioxide of generation, and use the deionized water of 220mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
2, peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 500W, ultrasonic 20min, making concentration is the suspension-s of graphene oxide in water of 2mg/mL.
3, through reductor graphene oxide is transformed to Graphene
(1), green reductor Quilonum Retard 200g of adding and 100g water mix in the suspension-s that reactions step 2 makes; The graphene oxide aqueous solution mixed with the green reductor aqueous solution in 1: 70 by volume, heated 100 ℃, and magnetic agitation mixes; Reaction times 3h; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene 2.6g and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is carried out underpressure distillation and is concentrated to the required concentration of reactions step 3,70 ℃ of distillation temperatures.The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because can not be contaminated, so can recycle green reductor for a long time.
Embodiment four
Based on green deoxy technology graphene preparation method, comprise following reactions step:
1, the intercalation oxidation of graphite
(1), take by weighing natural graphite 4g, SODIUMNITRATE 1g drops in the flask, slowly adds 98% vitriol oil 220mL, uses the thermostat water bath temperature control at 2 ℃, magnetic agitation makes uniform and stable the carrying out of reaction system.
(2), after question response step (1) carries out 10min, gradation slowly adds potassium permanganate 13g, magnetic agitation, temperature of reaction are controlled at 40 ℃.
(3), after reactions step (2) is carried out 10h, add deionized water 220mL, reaction system is carried out termination reaction, regulate temperature of reaction to 110 ℃ under the magnetic agitation.
(4), the question response step enters (3) and carries out 1.5h, reaction system steadily after, add ydrogen peroxide 50 20mL, remove the Manganse Dioxide of generation, and use the deionized water of 260mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
2, peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 400W, ultrasonic 15min, making concentration is the suspension-s of graphene oxide in water of 3mg/mL.
3, through reductor graphene oxide is transformed to Graphene
(1), in the suspension-s that reactions step 2 makes, add green reductor yellow soda ash and salt of wormwood respectively 50g mix and be dissolved in the 100g deionized water; The graphene oxide aqueous solution mixed with the green reductor aqueous solution in 60: 1 by volume, heated 110 ℃, and magnetic agitation mixes; Reaction times 30min; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene 2.2g and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is carried out underpressure distillation and is concentrated to the required concentration of reactions step 3,80 ℃ of distillation temperatures.The reactions step 3 that the liquid concentrator that obtains adds next group experiment recycles, because can not be contaminated, so can recycle green reductor for a long time.
Embodiment five
Based on green deoxy technology graphene preparation method, comprise following reactions step:
1, the intercalation oxidation of graphite
(1), take by weighing natural graphite 4g, SODIUMNITRATE 2g drops in the flask, slowly adds 98% vitriol oil 230mL, uses the thermostat water bath temperature control at 0 ℃, magnetic agitation makes uniform and stable the carrying out of reaction system.
(2), after question response step (1) carries out 1.5h, gradation slowly adds potassium permanganate 24g, magnetic agitation, temperature of reaction are controlled at 42 ℃.
(3), after reactions step (2) is carried out 15h, add deionized water 130mL, reaction system is carried out termination reaction, regulate temperature of reaction to 100 ℃ under the magnetic agitation.
(4), the question response step enters (3) and carries out 45min, reaction system steadily after, add ydrogen peroxide 50 40mL, remove the Manganse Dioxide of generation, and use the deionized water of 125mL that reaction system is carried out secondary dilution, obtain suspension-s; The insulation of use heating in water bath, magnetic agitation.
(5), suspension-s that reactions step (4) is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite.
2, peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that reactions step (5) is obtained and ionized water at room temperature, through the power of 300W, ultrasonic 13min, making concentration is the suspension-s of graphene oxide in water of 2mg/mL.
3, through reductor graphene oxide is transformed to Graphene
(1), in the suspension-s that reactions step 2 makes, add green reductor yellow soda ash, salt of wormwood and Quilonum Retard respectively 30g mix and be dissolved in the 90g deionized water; The graphene oxide aqueous solution mixed with the green reductor aqueous solution in 3: 1 by volume, heated 90 ℃, and magnetic agitation mixes; Reaction times 2h; Obtain reaction liquid, reaction system is sealed, and the carbonic acid gas that produces is collected.
(2), to the reaction liquid that reactions step (1) obtains, filtering separation obtains Graphene 2.4g and filtrating.
4, the recycling of green reductor
The filtrating that reactions step 3 is obtained is carried out underpressure distillation and is concentrated to the required concentration of reactions step 3,75 ℃ of distillation temperatures.The reactions step 3 that the liquid concentrator that obtains can add next group experiment recycles, because can not be contaminated, so can recycle green reductor for a long time.
Embodiment six
Repeat instance one, the green reductor after obtaining concentrating is recycled repeating instance for the second time for the moment, circulate 11 times always.
Claims (3)
1. preparation method of graphene based on green deoxy technology is characterized in that comprising following reactions step:
(1), the intercalation oxidation of graphite
1., press the proportioning of graphite and preoxidation agent, put into flask, press the proportioning of graphite and intercalation oxygenant, the intercalation oxygenant is slowly added, temperature control is to suitable temperature, magnetic agitation makes reaction system uniform and stable;
2., the proportioning of pressing graphite and strong oxidizer, with the strong oxidizer gradation slowly join reactions step 1. in, the rapid constant temperature of the temperature of reaction system is to suitable temperature, magnetic agitation is reacted to the suitable time;
3., after 2. reactions step finishes, add proper amount of deionized water reaction system carried out termination reaction, regulate temperature of reaction under the magnetic agitation to desired value, heat tracing, magnetic agitation;
4., the question response step 3. reaction system steadily after, the proportioning of press graphite and strong oxidizer, adding strong oxidizer, and use a certain amount of deionized water that reaction system is carried out secondary dilution. obtain suspension-s, heat tracing, magnetic agitation;
5., suspension-s that 4. reactions step is obtained, filtering separation, removal of impurities obtain the intercalation oxide compound of graphite;
(2), peeling off of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of the graphite that 5. reactions step is obtained at room temperature mixes with ionized water, and through suitable power, the regular hour is carried out ultra-sonic dispersion, makes the suspension-s of graphene oxide in water under the finite concentration;
(3), through green reductor graphene oxide is transformed to Graphene
1., in the suspension-s that reactions step (2) makes; By the aqueous solution of certain density green reductor and the proportioning of graphene oxide, add the aqueous solution of green reductor, magnetic agitation mixes; Under suitable temperature; Insulation reaction, deoxidation finishes behind the certain hour, obtains reaction liquid; Reaction system is sealed, and the carbonic acid gas that produces is collected;
2., to the reaction liquid that 1. reactions step obtains, filtering separation obtains Graphene and filtrating;
(4), the recycling of green reductor
The filtrating that reactions step (3) is obtained is placed in the round-bottomed flask, adds zeolite and under suitable temperature, carries out underpressure distillation, is concentrated to the required concentration of reactions step (3); The reactions step (3) that the liquid concentrator that obtains adds next group experiment recycles, because reaction system can not polluted green reductor, so can recycle green reductor for a long time.
2. according to claim 1 a kind of based on green deoxy technology preparation method of graphene, it is characterized in that described graphite is the loose oxidation of intercalation or natural graphite of peeling off and the expanded graphite be convenient to of laminated structure; Described intercalation oxygenant is 98% vitriol oil; Described preoxidation agent is a SODIUMNITRATE; Described strong oxidizer is potassium permanganate or ydrogen peroxide 50; Described green reductor is one or more in yellow soda ash or salt of wormwood or the Quilonum Retard.
3. according to claim 1 a kind of based on green deoxy technology preparation method of graphene; It is characterized in that the aqueous solution of described graphite and preoxidation agent, graphite and strong oxidizer, graphite and intercalation oxygenant, green reductor and the proportioning of water, green reductor and the proportioning of graphene oxide; In dry weight part, as follows:
The proportioning of graphite and preoxidation agent 1: 0.2～1: 1; The proportioning of graphite and strong oxidizer 1: 3～1: 6; The proportioning of graphite and intercalation oxygenant 1: 30～1: 60; The proportioning of green reductor and water 0.05: 1～3.2: 1; The aqueous solution of green reductor and the proportioning of graphene oxide 1: 100～100: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072980A (en) * | 2013-02-05 | 2013-05-01 | 哈尔滨理工大学 | Method for quickly preparing graphene sheets |
| US20150298977A1 (en) * | 2012-11-21 | 2015-10-22 | Grapheneall Co., Ltd. | Method for forming graphene quantum dot |
| CN109133042A (en) * | 2018-09-10 | 2019-01-04 | 宁波革鑫新能源科技有限公司 | A kind of preparation method of sheet diameter graphene film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| CN102001651A (en) * | 2010-12-30 | 2011-04-06 | 上海交通大学 | Method for preparing graphene based on hydroxylamine reduction |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102167314A (en) * | 2011-05-23 | 2011-08-31 | 浙江大学 | Method for preparing graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966988A (en) * | 2010-11-17 | 2011-02-09 | 哈尔滨工业大学 | Method for preparing graphene powder |
| CN102001651A (en) * | 2010-12-30 | 2011-04-06 | 上海交通大学 | Method for preparing graphene based on hydroxylamine reduction |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102167314A (en) * | 2011-05-23 | 2011-08-31 | 浙江大学 | Method for preparing graphene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150298977A1 (en) * | 2012-11-21 | 2015-10-22 | Grapheneall Co., Ltd. | Method for forming graphene quantum dot |
| CN103072980A (en) * | 2013-02-05 | 2013-05-01 | 哈尔滨理工大学 | Method for quickly preparing graphene sheets |
| CN103072980B (en) * | 2013-02-05 | 2016-08-17 | 哈尔滨理工大学 | The method quickly preparing graphene platelet |
| CN109133042A (en) * | 2018-09-10 | 2019-01-04 | 宁波革鑫新能源科技有限公司 | A kind of preparation method of sheet diameter graphene film |
| CN109133042B (en) * | 2018-09-10 | 2020-06-05 | 宁波革鑫新能源科技有限公司 | Preparation method of large-sheet-diameter graphene sheet |
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