CN102557018B - A kind of based on green deoxidation technology graphene preparation method - Google Patents
A kind of based on green deoxidation technology graphene preparation method Download PDFInfo
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- CN102557018B CN102557018B CN201110426540.2A CN201110426540A CN102557018B CN 102557018 B CN102557018 B CN 102557018B CN 201110426540 A CN201110426540 A CN 201110426540A CN 102557018 B CN102557018 B CN 102557018B
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Abstract
The invention discloses a kind of based on green deoxidation technology graphene preparation method, graphene oxide is prepared in the intercalation oxidation comprising graphite; Complete graphene oxide by green reductor to transform to Graphene; The green reductor that the present invention adopts, just can prepare Graphene fast, in batches by heating, and reductor recoverable, reaction end gas is single, is convenient to collect, and reaches the production object of green low-carbon; Deoxidation section of the present invention is easy and simple to handle, and safety is with low cost, zero release.
Description
[technical field]
The present invention relates to the preparation method of two-dimension nano materials, particularly a kind of method preparing single-layer graphene based on green deoxidation technology batch.
[background technology]
Graphene is a kind of by the tightly packed two dimensional crystal formed of carbon atom, is the essentially consist unit of allotropic substance of carbon comprising soccerballene, carbon nanotube, graphite.Graphene has the characteristics such as special optics, electricity, calorifics, mechanics, and it has second integer quantum Hall effect of room temperature, quantum tunneling effect, electronic mobility 20000m at a high speed
2v
-1s
-1, high heat conductance 3000Wm
-1k
-1with outstanding mechanical property (high-modulus 1060GPa, high strength 130GPa).The nanoelectronics and spintronics components and parts of respectively providing the energy that has specific characteristics can not only be made with these characteristic Graphenes, and utilize its two dimensional structure, the semiconductor lithography process of standard can be used to carry out the design of large-scale integrated nano-electron circuit, make the 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 based upon on the basis of its scale operation.Therefore research emphasis is placed in the suitability for industrialized production of Graphene by a large amount of scientist both at home and abroad.The method that Graphene is peeled off by micromechanics by English physicist An Deliehaimu and Constantine Nuo Woxiaoluofu the earliest successfully obtains, and the maximum shortcoming of the method yields poorly.The preparation method of Graphene can be divided into 4 large classes up till now: micromechanics stripping method, and chemical Vapor deposition process, epitaxial growth method, prepares soliquid method.But due to the hydrophobicity of Graphene self, and the character of reunion in a solvent all creates restriction to its preparation.From with short production cycle in performance obtained in laboratory research, and the high angle of output is set out, and thinks that the wet chemical oxidation-reduction method prepared in soliquid method has the potentiality of scale operation in the world.
Wet chemical oxidation-reduction method refers to and first graphite raw material oxidation is obtained graphite oxide, by peeling off obtained graphene oxide, and the method restored.Conventional method for oxidation only has three kinds: Brodie, Staudenmaier or Hummers, method of reducing is then studied more, conventional method of reducing has chemical liquid phase reduction, plasma method reduction, thermal reduction, the stripping of hydrogen arc-over, photoreduction, microwave reduction etc., conventional is chemical reduction, hydrazine hydrate, H
2, NaBH
4, vitamins C, quadrol, Na/CH
3oH etc.But these methods can in the face of reductive agent high toxicity and can not recycle, reaction time length, high energy consumption, tail gas directly discharges problems such as cannot processing, thus brings obstruction to suitability for industrialized production.
[summary of the invention]
For the deficiency of existing graphene preparation method, the object of the present invention is to provide a kind of preparation method that can solve the Graphene based on green deoxidation technology of following technical problem:
Selecting 1, by reductor, as selected sodium carbonate, salt of wormwood etc., realize reductor cyclic production, nontoxic, the deoxidation process of the graphene oxide of zero release;
2, the reaction times of deoxidation process is reduced;
3, by introducing the weakly alkaline of carbonate, the stability of Graphene at aqueous phase system is improved.
In order to realize above-mentioned goal of the invention, the present invention adopts following technical scheme:
1, the intercalation oxidation of graphite;
2, the stripping of graphite oxide obtains graphene oxide;
3, by reductor, graphene oxide is transformed to Graphene;
4, the tail gas that green deoxidation process produces is pure carbon dioxide, directly can recycle, realize zero carbon emission.
Specific embodiment of the invention scheme is as follows:
1, the intercalation oxidation of graphite
(1), by the proportioning of graphite and preoxidation agent, flask is put into; By the proportioning of graphite and intercalation oxygenant, slowly added by intercalation oxygenant, temperature control is to suitable temperature, and magnetic agitation, the carrying out making reaction system uniform and stable reacts.
(2), by the proportioning of graphite and strong oxidizer, strong oxidizer gradation is slowly added in reactions steps (1); The rapid constant temperature of temperature of reaction system is to suitable temperature, and magnetic agitation, is reacted to the suitable time.
(3), after reactions steps (2) terminates, add appropriate deionized water and reaction terminating is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to arrive suitable value, heating and thermal insulation, magnetic agitation.
(4), question response step (3) reaction system steadily after, by the proportioning of graphite and strong oxidizer, add strong oxidizer, and use a certain amount of deionized water to carry out secondary dilution to reaction system, obtain suspension. heating and thermal insulation, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
2, the stripping of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of graphite reactions steps (5) obtained is distributed in appropriate water, and by suitable power, the regular hour carries out ultrasonic disperse, the suspension of graphene oxide in water under obtained finite concentration.
3, by reductor, graphene oxide is transformed to Graphene
(1), in the suspension that reactions steps 2 is obtained, by the certain density aqueous solution of green reductor and the proportioning of graphene oxide, add the aqueous solution of green reductor, magnetic agitation mixes, at a proper temperature, insulation reaction, after certain hour, deoxidation terminates, and obtains reaction liquid; Reaction system is closed, and the carbonic acid gas produced is collected.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene and filtrate.
4, the recycling of green reductor
Be placed in round-bottomed flask to the filtrate that reactions steps 3 obtains, add zeolite and carry out underpressure distillation at a proper temperature, be concentrated to the concentration needed for reactions steps 3, the reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, because reaction system can not pollute green reductor, so green reductor can be recycled for a long time.
The preparation method of Graphene of the present invention, as graphite, optional natural graphite, synthetic graphite, expanded graphite, preferred laminated structure is loosened and is convenient to the oxidation of intercalation or the natural graphite of stripping and expanded graphite; As intercalation oxygenant, the optional vitriol oil, phosphoric acid, preferably 98% vitriol oil; As preoxidation agent, optional SODIUMNITRATE, saltpetre, preferred SODIUMNITRATE; As strong oxidizer, optional potassium permanganate, oxygen acid potassium, SODIUMNITRATE, hydrogen peroxide, preferred potassium permanganate or hydrogen peroxide; As green reductor, optional carbonate material, one or more in preferred sodium carbonate, salt of wormwood, Quilonum Retard.
The proportioning of 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 graphene oxide (in dry weight part, lower with) is:
The proportioning 1: 10 ~ 1: 100 of graphite and intercalation oxygenant, preferably 1: 30 ~ 1: 60; The proportioning 1: 0 ~ 1: 2 of graphite and preoxidation agent, preferably 1: 0.2 ~ 1: 1; The proportioning 1: 2 ~ 1: 7 of graphite and strong oxidizer, preferably 1: 3 ~ 1: 6; The proportioning 0.005: 1 ~ 3.2: 1 of green reductor and water, preferably 0.05: 1 ~ 3.2: 1; The green aqueous solution of reductor and the proportioning 1: 200 ~ 100: 2 of graphene oxide, preferably 1: 100 ~ 100: 1.
Therefore, the preparation method of a kind of Graphene based on green deoxidation technology of the present invention, preferably adopts following embodiment:
1, the intercalation oxidation of graphite
(1), by natural graphite or expanded graphite: the proportioning 1: 0.2 ~ 1: 1 of SODIUMNITRATE, take natural graphite or expanded graphite and SODIUMNITRATE, and feed intake in flask, by natural graphite or expanded graphite: the proportioning 1: 30 ~ 1: 60 of 98% vitriol oil, slowly add 98% vitriol oil, temperature of reaction controls at 0 ~ 5 DEG C, and magnetic agitation makes reaction system uniform and stable.
(2), after question response step (1) carries out 10min ~ 2h, by natural graphite or expanded graphite: the proportioning 1: 3 ~ 1: 6 of potassium permanganate, gradation slowly adds potassium permanganate; Magnetic agitation, temperature of reaction controls at 25 ~ 45 DEG C
(3), after reactions steps (2) carries out 2h ~ 36h, add deionized water 100 ~ 300mL, termination reaction, under magnetic agitation, regulate temperature of reaction to 40 ~ 120 DEG C.
(4), question response step (3) carries out 10mim ~ 2h, after reaction system is steady, add hydrogen peroxide 10 ~ 50mL, the Manganse Dioxide that removing produces, and use the deionized water of 120-280mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
The stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 50 ~ 500W, ultrasonic 2 ~ 30min, obtains the suspension of graphene oxide in water for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), in the suspension that reactions steps 2 is obtained, by the volume ratio 1: 100 ~ 100: 1 of the graphene oxide aqueous solution and the green reductor aqueous solution (proportioning 0.05: 1 ~ 3.2: 1 of green reductor and water), add one or more the aqueous solution in green reductor sodium carbonate, salt of wormwood, Quilonum Retard, be heated to 50 ~ 120 DEG C, magnetic agitation, mix, reaction times 3min ~ 5h, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene and filtrate.
4, the recycling of green reductor
Be placed in round-bottomed flask to the filtrate that reactions steps 3 obtains, add zeolite and carry out underpressure distillation at 40 ~ 130 DEG C, be concentrated to the concentration needed for reactions steps 3; The reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, because reaction system can not pollute green reductor, so can recycle green reductor for a long time.
[effect of the present invention]
The green reductor that the present invention adopts is under aqueous conditions, just can be quick by heated and stirred under lesser temps, batch prepare Graphene by entering deoxidation to graphene oxide, green reductor itself can be recycled by underpressure distillation under lesser temps, the tail gas of deoxidation process generation is simultaneously single, consist of carbonic acid gas, be convenient to collect, thus reach the production object 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, not easily reunites, and carbon-carbon double bond retains more, possesses high connductivity potentiality.
[specific embodiments]
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within limited range of the present invention equally after the content of having read the present invention's instruction.Ratio range in embodiment is the ratio of dry weight.
Embodiment one
Based on green deoxidation technology graphene preparation method, comprise following reactions steps:
1, the intercalation oxidation of graphite
(1), take natural graphite 4g, SODIUMNITRATE 3g, drop in flask, slowly add 98% vitriol oil 120mL, use thermostat water bath temperature control at 0 DEG C, magnetic agitation, makes the carrying out that reaction system is uniform and stable.
(2), after question response step (1) carries out 1h, gradation slowly adds potassium permanganate 20g, magnetic agitation, and temperature of reaction controls at 30 DEG C.
(3), after reactions steps (2) carries out 24h, add deionized water 100mL, termination reaction is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to 75 DEG C.
(4), question response step enters (3) and carries out 20mim, reaction system steadily after, add hydrogen peroxide 35mL, the Manganse Dioxide that removing produces, and use the deionized water of 150mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite
The stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 200W, ultrasonic 10min, obtained concentration is the suspension of graphene oxide in water of 2mg/mL for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), in the suspension that reactions steps 2 is obtained, add green reductor salt of wormwood 100g to mix with 100g water, the graphene oxide aqueous solution and the green reductor aqueous solution to mix by volume at 1: 1, heat 70 DEG C, magnetic agitation mixes, reaction times 5min, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene 2.5g and filtrate.
4, the recycling of green reductor
The filtrate obtained reactions steps 3 is carried out underpressure distillation and is concentrated to concentration needed for reactions steps 3, distillation temperature 60 DEG C.The reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, due to can not be contaminated, so can recycle green reductor for a long time.
Embodiment two
Based on green deoxidation technology graphene preparation method, comprise following reactions steps:
1, the intercalation oxidation of graphite
(1), take expanded graphite 4g, SODIUMNITRATE 2g, drop in flask, slowly add 98% vitriol oil 160mL, use thermostat water bath temperature control at 3 DEG C, magnetic agitation, makes the carrying out that reaction system is uniform and stable.
(2), after question response step (1) carries out 30min, gradation slowly adds potassium permanganate 22g, magnetic agitation, and temperature of reaction controls at 26 DEG C.
(3), after reactions steps (2) carries out 5h, add deionized water 200mL, termination reaction is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to 45 DEG C.
(4), question response step enters (3) and carries out 1h, reaction system steadily after, add hydrogen peroxide 15mL, the Manganse Dioxide that removing produces, and use the deionized water of 150mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
2, the stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 60W, ultrasonic 30min, obtained concentration is the suspension of graphene oxide in water of 2mg/mL for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), in the suspension that reactions steps 2 is obtained, add green reductor sodium carbonate 150g to mix with 100g water, the graphene oxide aqueous solution and the green reductor aqueous solution to mix by volume at 10: 1, heat 55 DEG C, magnetic agitation mixes, reaction times 5h, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene 2.7g and filtrate.
4, the recycling of green reductor
The filtrate obtained reactions steps 3 is carried out underpressure distillation and is concentrated to concentration needed for reactions steps 3, distillation temperature 70 DEG C.The reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, due to can not be contaminated, so can recycle green reductor for a long time.
Embodiment three
Based on green deoxidation technology graphene preparation method, comprise following reactions steps:
1, the intercalation oxidation of graphite
(1), take expanded graphite 4g, SODIUMNITRATE 1g, drop in flask, slowly add 98% vitriol oil 200mL, use thermostat water bath temperature control at 5 DEG C, magnetic agitation, makes the carrying out that reaction system is uniform and stable.
(2), after question response step (1) carries out 2h, gradation slowly adds potassium permanganate 17g, magnetic agitation, and temperature of reaction controls at 35 DEG C.
(3), after reactions steps (2) carries out 7h, add deionized water 300mL, termination reaction is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to 90 DEG C.
(4), question response step enters (3) and carries out 2h, reaction system steadily after, add hydrogen peroxide 35mL, the Manganse Dioxide that removing produces, and use the deionized water of 220mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
2, the stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 500W, ultrasonic 20min, obtained concentration is the suspension of graphene oxide in water of 2mg/mL for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), in the suspension that reactions steps 2 is obtained, add green reductor Quilonum Retard 200g to mix with 100g water, the graphene oxide aqueous solution and the green reductor aqueous solution to mix by volume at 1: 70, heat 100 DEG C, magnetic agitation mixes, reaction times 3h, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene 2.6g and filtrate.
4, the recycling of green reductor
The filtrate obtained reactions steps 3 is carried out underpressure distillation and is concentrated to concentration needed for reactions steps 3, distillation temperature 70 DEG C.The reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, due to can not be contaminated, so can recycle green reductor for a long time.
Embodiment four
Based on green deoxidation technology graphene preparation method, comprise following reactions steps:
1, the intercalation oxidation of graphite
(1), take natural graphite 4g, SODIUMNITRATE 1g, drop in flask, slowly add 98% vitriol oil 220mL, use thermostat water bath temperature control at 2 DEG C, magnetic agitation, makes the carrying out that reaction system is uniform and stable.
(2), after question response step (1) carries out 10min, gradation slowly adds potassium permanganate 13g, magnetic agitation, and temperature of reaction controls at 40 DEG C.
(3), after reactions steps (2) carries out 10h, add deionized water 220mL, termination reaction is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to 110 DEG C.
(4), question response step enters (3) and carries out 1.5h, reaction system steadily after, add hydrogen peroxide 20mL, the Manganse Dioxide that removing produces, and use the deionized water of 260mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
2, the stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 400W, ultrasonic 15min, obtained concentration is the suspension of graphene oxide in water of 3mg/mL for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), add in the suspension that reactions steps 2 is obtained green reductor sodium carbonate and salt of wormwood respectively 50g mix and be dissolved in 100g deionized water, the graphene oxide aqueous solution and the green reductor aqueous solution to mix by volume at 60: 1, heat 110 DEG C, magnetic agitation mixes, reaction times 30min, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene 2.2g and filtrate.
4, the recycling of green reductor
The filtrate obtained reactions steps 3 is carried out underpressure distillation and is concentrated to concentration needed for reactions steps 3, distillation temperature 80 DEG C.The reactions steps 3 that the concentrated solution obtained adds next group experiment recycles, due to can not be contaminated, so can recycle green reductor for a long time.
Embodiment five
Based on green deoxidation technology graphene preparation method, comprise following reactions steps:
1, the intercalation oxidation of graphite
(1), take natural graphite 4g, SODIUMNITRATE 2g, drop in flask, slowly add 98% vitriol oil 230mL, use thermostat water bath temperature control at 0 DEG C, magnetic agitation, makes the carrying out that reaction system is uniform and stable.
(2), after question response step (1) carries out 1.5h, gradation slowly adds potassium permanganate 24g, magnetic agitation, and temperature of reaction controls at 42 DEG C.
(3), after reactions steps (2) carries out 15h, add deionized water 130mL, termination reaction is carried out to reaction system, under magnetic agitation, regulate temperature of reaction to 100 DEG C.
(4), question response step enters (3) and carries out 45min, reaction system steadily after, add hydrogen peroxide 40mL, the Manganse Dioxide that removing produces, and use the deionized water of 125mL to carry out secondary dilution to reaction system, obtain suspension; Use heating in water bath is incubated, magnetic agitation.
(5) suspension, by reactions steps (4) obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite.
2, the stripping of the intercalation oxide compound of graphite obtains graphene oxide
At room temperature, by the power of 300W, ultrasonic 13min, obtained concentration is the suspension of graphene oxide in water of 2mg/mL for the intercalation oxide compound of graphite reactions steps (5) obtained and ionized water.
3, by reductor, graphene oxide is transformed to Graphene
(1), add in the suspension that reactions steps 2 is obtained green reductor sodium carbonate, salt of wormwood and Quilonum Retard respectively 30g mix and be dissolved in 90g deionized water, the graphene oxide aqueous solution and the green reductor aqueous solution to mix by volume at 3: 1, heat 90 DEG C, magnetic agitation mixes, reaction times 2h, obtain reaction liquid, reaction system is closed, and collects the carbonic acid gas produced.
(2) reaction liquid, to reactions steps (1) obtained, filtering separation, obtains Graphene 2.4g and filtrate.
4, the recycling of green reductor
The filtrate obtained reactions steps 3 is carried out underpressure distillation and is concentrated to concentration needed for reactions steps 3, distillation temperature 75 DEG C.The reactions steps 3 that the concentrated solution obtained can add next group experiment recycles, due to can not be contaminated, so can recycle green reductor for a long time.
Embodiment six
Repeat example one, recycling obtaining the green reductor after concentrating for the moment at second time repetition example, circulating 11 times always.
Claims (2)
1., based on a preparation method for the Graphene of green deoxidation technology, it is characterized in that comprising following reactions steps:
(1), the intercalation oxidation of graphite
1., by the proportioning of graphite and preoxidation agent, put into flask, by the proportioning of graphite and intercalation oxygenant, slowly added by intercalation oxygenant, temperature control is to suitable temperature, and magnetic agitation, makes reaction system uniform and stable; Described graphite is that laminated structure is loosened and is convenient to the oxidation of intercalation or the natural graphite of stripping and expanded graphite; Described intercalation oxygenant is 98% vitriol oil; Described preoxidation agent is SODIUMNITRATE;
2., by the proportioning of graphite and strong oxidizer, strong oxidizer gradation is slowly joined reactions steps 1. in, the rapid constant temperature of temperature of reaction system is to suitable temperature, and magnetic agitation, is reacted to the suitable time; Described strong oxidizer is potassium permanganate or hydrogen peroxide;
3., after 2. reactions steps terminates, add appropriate deionized water and termination reaction is carried out to reaction system, regulate temperature of reaction to arrive desired value under magnetic agitation, heating and thermal insulation, magnetic agitation;
4., question response step 3. reaction system steadily after, by the proportioning of graphite and strong oxidizer, add strong oxidizer, and use a certain amount of deionized water to carry out secondary dilution to reaction system. obtain suspension, heating and thermal insulation, magnetic agitation;
5. the suspension, by reactions steps 4. obtained, filtering separation, removal of impurities, obtain the intercalation oxide compound of graphite;
(2), the stripping of the intercalation oxide compound of graphite obtains graphene oxide
The intercalation oxide compound of graphite reactions steps 5. obtained at room temperature mixes with ionized water, and by suitable power, the regular hour carries out ultrasonic disperse, the suspension of graphene oxide in water under obtained finite concentration;
(3), by green reductor, graphene oxide is transformed to Graphene
1., in the suspension, in reactions steps (2) obtained, by the certain density aqueous solution of green reductor and the proportioning of graphene oxide, the aqueous solution of green reductor is added, magnetic agitation mixes, at a proper temperature, and insulation reaction, after certain hour, deoxidation terminates, and obtains reaction liquid; Reaction system is closed, and collects the carbonic acid gas produced; Described green reductor is one or more in sodium carbonate or salt of wormwood or Quilonum Retard;
2. the reaction liquid, to reactions steps 1. obtained, filtering separation, obtains Graphene and filtrate;
(4), the recycling of green reductor
Be placed in round-bottomed flask to the filtrate that (3) reactions steps obtains, add zeolite and carry out underpressure distillation at a proper temperature, be concentrated to the concentration that reactions steps is (3) required; (3) the reactions steps that the concentrated solution obtained adds next group experiment recycles, because reaction system can not pollute green reductor, so can recycle green reductor for a long time.
2. the preparation method of a kind of Graphene based on green deoxidation technology according to claim 1, it is characterized in that described graphite and preoxidation agent, graphite and strong oxidizer, graphite and intercalation oxygenant, the proportioning of green reductor and water, the aqueous solution of green reductor and the proportioning of graphene oxide, in dry weight part, as follows:
Proportioning 1:0.2 ~ the 1:1 of graphite and preoxidation agent; Proportioning 1:3 ~ the 1:6 of graphite and strong oxidizer; Proportioning 1:30 ~ the 1:60 of graphite and intercalation oxygenant; Proportioning 0.05:1 ~ the 3.2:1 of green reductor and water; The green aqueous solution of reductor and the proportioning 1:100 ~ 100:1 of graphene oxide.
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| 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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| 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 |
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