CN105271192A - Preparation method of modified graphene - Google Patents
Preparation method of modified graphene Download PDFInfo
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Abstract
The invention discloses a preparation method of modified graphene, relates to a preparation method of graphene and aims to solve the technical problems of high preparation cost, complicated process, single and low functionalization degree and serious environment pollution when graphene is prepared with an existing oxidation-reduction method. The preparation method comprises 1), oxidation treatment of graphite; 2), preparation of a benzophenone hydrazine derivative; 3), preparation of a diaryl diazomethane derivative; 4), preparation of modified graphene. According to the preparation method, a functional group is introduced to a reaction of high-activity carbine and graphite oxide, the functional modification degree is improved, the preparation process is simplified, and the preparation method is suitable for large-scale industrial production and follow-up application.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene.
Background technology
Graphene is the material of the individual layer bi-dimensional cellular shape crystalline network that carbon atom is formed, and it has the performance of many excellences, as high Young's modulus and carrier mobility, huge specific surface area, excellent thermal conductivity and light transmission etc.Grapheme material demonstrates wide application prospect in fields such as support of the catalyst, flexible photoelectric device, biomaterial, sensing materials.At present, the preparation method of Graphene mainly contains micromechanics partition method, epitaxial growth method, chemical vapour deposition, graphite oxide reduction method etc.Wherein, graphite oxide reduction method prepares a kind of the most widely used method of Graphene so far.Graphite oxide reduction method, as a kind of low cost, the chemical process that can realize Graphene batch production, is subject to the great attention of relevant technical worker.But, oxidation reduction process needs to use the oxidizing species such as a large amount of strong acid, potassium permanganate, hydrogen peroxide, and the functional group introduced is generally containing oxygen functional group, thus cause that preparation cost is high, complex process, functionalization degree are single and on the low side, environmental pollution is serious, is thus not suitable for large-scale industrial production.
Summary of the invention
The present invention is that preparation cost when existing oxidation reduction process prepares Graphene is high in order to solve, complex process, functionalization degree is single and on the low side, environmental pollution is serious technical problem, and provides
a kind of preparation method of modified graphene.
Of the present invention
a kind of preparation method of modified graphenecarry out according to the following steps:
One, the oxide treatment of graphite: add the vitriol oil that 0.3L ~ 3L massfraction is 98% in the reactor of drying, under the condition stirred, add 10g ~ 100g Graphite Powder 99,0.1L ~ 1L massfraction are the concentrated nitric acid of 65%, ultrasonic 10min ~ 60min, be be incubated 10min ~ 100min under the condition of 20 DEG C ~ 60 DEG C in temperature, filter, the solid distilled water repetitive scrubbing obtained 3 times ~ 5 times, dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtains graphite oxide;
Two, the preparation of benzophenone hydrazone derivative: the benzophenone derivates of 2g ~ 20g is joined in round-bottomed flask, add 50mL ~ 1000mL dehydrated alcohol successively and 1g ~ 50g massfraction is the hydrazine hydrate solution of 85%, to reflux 24h ~ 72h under temperature is 80 DEG C and the condition that stirs, then underpressure distillation goes out to add the dehydrated alcohol of dehydrated alcohol volume 40% ~ 60%, remaining reaction solution is crystallisation by cooling 10min ~ 60min in ice-water bath, suction filtration product, the solid distilled water wash obtained 3 times ~ 5 times, be dry 12h ~ 36h under the condition of 20 DEG C ~ 60 DEG C in vacuum and temperature, obtain benzophenone hydrazone derivative,
Three, the preparation of two aryldiazonium methane Derivatives: benzophenone hydrazone derivative 0.1g ~ 5g step 2 obtained is added in the round-bottomed flask that 5mL ~ 200mL tetrahydrofuran (THF) is housed, then add the anhydrous sodium sulphate of 0.1g ~ 10g, the MnO of 0.1g ~ 10g successively
2with the alcohol saturated solution of the KOH of 0.1mL ~ 10mL, 1h ~ 12h is stirred under the condition of room temperature lucifuge, employing sand core funnel filters, with methylene dichloride repetitive scrubbing 3 times ~ 5 times, the filtrate obtained is dry 12h ~ 36h under vacuum and temperature are the condition of 20 DEG C ~ 60 DEG C, obtains two aryldiazonium methane Derivatives;
Four, the preparation of modified graphene: two aryldiazonium methane Derivatives 0.1g ~ 5g step 3 obtained are added in the round-bottomed flask that 10mL ~ 1000mL methylene dichloride is housed, add the graphite oxide that 0.1g ~ 50g step one obtains again, lucifuge underpressure distillation goes out whole solvent, gained solid is incubated 10min ~ 120min under temperature is the condition of 100 DEG C ~ 200 DEG C, by washed with dichloromethane 3 ~ 5 times, with distilled water wash 3 ~ 5 times, the solid dispersal obtained in acetone, ultrasonic disperse 1h ~ 6h, suction filtration, the solid obtained is dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtain modified graphene.
The present invention adopts nitration mixture to carry out appropriate oxide treatment to graphite, introducing portion is containing oxygen functional group, with two aryl ketone derivative for raw material, via hydrazone and the two aryldiazonium methane Derivatives of oxidizing reaction preparation, under heating or illumination condition, two aryldiazonium methane Derivatives can remove diazonium groups and generate high
gaccabbeen, utilizes the insertion reaction of carbon Cabbeen and graphite oxide and the introducing of addition reaction practical function group, adopts the means of ultrasonic stripping to obtain modified graphene further.
Preparation method of the present invention utilizes the reaction of high reactivity Cabbeen and graphite oxide to introduce functional group, improves functional modification degree, simplifies preparation technology, is applicable to large-scale commercial production and follow-up application.
Accompanying drawing explanation
fig. 1that the modified graphene that 50mg test one prepares is dissolved in 500mL dehydrated alcohol the TEM photo tested and obtain.
Embodiment:
Embodiment one: this enforcement side is
a kind of preparation method of modified graphene, specifically carry out according to the following steps:
One, the oxide treatment of graphite: add the vitriol oil that 0.3L ~ 3L massfraction is 98% in the reactor of drying, under the condition stirred, add 10g ~ 100g Graphite Powder 99,0.1L ~ 1L massfraction are the concentrated nitric acid of 65%, ultrasonic 10min ~ 60min, be be incubated 10min ~ 100min under the condition of 20 DEG C ~ 60 DEG C in temperature, filter, the solid distilled water repetitive scrubbing obtained 3 times ~ 5 times, dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtains graphite oxide;
Two, the preparation of benzophenone hydrazone derivative: the benzophenone derivates of 2g ~ 20g is joined in round-bottomed flask, add 50mL ~ 1000mL dehydrated alcohol successively and 1g ~ 50g massfraction is the hydrazine hydrate solution of 85%, to reflux 24h ~ 72h under temperature is 80 DEG C and the condition that stirs, then underpressure distillation goes out to add the dehydrated alcohol of dehydrated alcohol volume 40% ~ 60%, remaining reaction solution is crystallisation by cooling 10min ~ 60min in ice-water bath, suction filtration product, the solid distilled water wash obtained 3 times ~ 5 times, be dry 12h ~ 36h under the condition of 20 DEG C ~ 60 DEG C in vacuum and temperature, obtain benzophenone hydrazone derivative,
Three, the preparation of two aryldiazonium methane Derivatives: benzophenone hydrazone derivative 0.1g ~ 5g step 2 obtained is added in the round-bottomed flask that 5mL ~ 200mL tetrahydrofuran (THF) is housed, then add the anhydrous sodium sulphate of 0.1g ~ 10g, the MnO of 0.1g ~ 10g successively
2with the alcohol saturated solution of the KOH of 0.1mL ~ 10mL, 1h ~ 12h is stirred under the condition of room temperature lucifuge, employing sand core funnel filters, with methylene dichloride repetitive scrubbing 3 times ~ 5 times, the filtrate obtained is dry 12h ~ 36h under vacuum and temperature are the condition of 20 DEG C ~ 60 DEG C, obtains two aryldiazonium methane Derivatives;
Four, the preparation of modified graphene: two aryldiazonium methane Derivatives 0.1g ~ 5g step 3 obtained are added in the round-bottomed flask that 10mL ~ 1000mL methylene dichloride is housed, add the graphite oxide that 0.1g ~ 50g step one obtains again, lucifuge underpressure distillation goes out whole solvent, gained solid is incubated 10min ~ 120min under temperature is the condition of 100 DEG C ~ 200 DEG C, by washed with dichloromethane 3 ~ 5 times, with distilled water wash 3 ~ 5 times, the solid dispersal obtained in acetone, ultrasonic disperse 1h ~ 6h, suction filtration, the solid obtained is dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtain modified graphene.
Embodiment two: the difference of present embodiment and embodiment one is: the benzophenone derivates described in step 2 is benzophenone, 4-phenyl benzophenone or 3,4-dimethyl benzophenone.Other are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one or two is: the benzophenone derivates described in step 2 is 4,4'-dimethoxy-benzophenone, 4, two (dimethylamino) benzophenone of 4'-or two (dimethylamino) thiobenzophenon of 4,4'-.Other are identical with embodiment one or two.
Embodiment four: the difference of present embodiment and embodiment one to three is: the benzophenone derivates described in step 2 is 4-methyl benzophenone, 4-methoxy benzophenone or 3,4-dimethyl benzophenone.Other are identical with embodiment one to three.
Embodiment five: the difference of present embodiment and embodiment one to four is: the benzophenone derivates described in step 2 is two (diethylin) benzophenone of 4,4'-dimethyl benzophenone or 4,4'-.Other are identical with embodiment one to four.
Test one: this test is
a kind of preparation method of modified graphene, specifically carry out according to the following steps:
One, the oxide treatment of graphite: add the vitriol oil that 1L massfraction is 98% in the reactor of drying, under the condition stirred, add 10g Graphite Powder 99,0.1L massfraction are the concentrated nitric acid of 65%, ultrasonic 30min, be be incubated 40min under the condition of 45 DEG C in temperature, filter, the solid distilled water repetitive scrubbing obtained 5 times, dry 24h under the condition of vacuum and subzero 20 DEG C, obtains graphite oxide;
Two, the preparation of benzophenone hydrazone derivative: the benzophenone derivates of 2g is joined in round-bottomed flask, add 50mL dehydrated alcohol successively and 4.5g massfraction is the hydrazine hydrate solution of 85%, to reflux 48h under temperature is 80 DEG C and the condition that stirs, then underpressure distillation goes out 30mL ethanol, remaining reaction solution is crystallisation by cooling 20min in ice-water bath, suction filtration product, the solid distilled water wash obtained 5 times, dry 24h under vacuum and temperature are the condition of 40 DEG C, obtains benzophenone hydrazone derivative;
Three, the preparation of two aryldiazonium methane Derivatives: benzophenone hydrazone derivative 0.25g step 2 obtained is added in the round-bottomed flask that 10mL tetrahydrofuran (THF) is housed, then add the anhydrous sodium sulphate of 0.25g, the MnO of 0.25g successively
2with the alcohol saturated solution of the KOH of 0.2mL, under the condition of room temperature lucifuge, stir 15h, adopt sand core funnel to filter, with methylene dichloride repetitive scrubbing 5 times, the filtrate obtained is dry 24h under vacuum and temperature are the condition of 40 DEG C, obtains two aryldiazonium methane Derivatives;
Four, the preparation of modified graphene: two aryldiazonium methane Derivatives 0.25g step 3 obtained are added in the round-bottomed flask that 30mL methylene dichloride is housed, add the graphite oxide that 1g step one obtains again, lucifuge underpressure distillation goes out whole solvent, gained solid is incubated 30min under temperature is the condition of 150 DEG C, by washed with dichloromethane 5 times, with distilled water wash 5 times, the solid dispersal obtained in acetone, ultrasonic disperse 3h, suction filtration, the solid obtained is dry 24h under the condition of vacuum and subzero 20 DEG C, obtains modified graphene.
Benzophenone derivates described in step 2 is 4,4'-dimethoxy-benzophenone.
The modified graphene prepared by 50mg is dissolved in 500mL dehydrated alcohol,
fig. 1test the TEM photo obtained, from
in figurecan find out that modified graphene prepared by test one can be dispersed and present multi-ply layer structure in ethanolic soln.Thus illustrate that modified graphene prepared by the present invention all has good dispersiveness in water, ethanol and acetone equal solvent.
XPS result shows, and the oxygen level of modified graphene prepared by the present invention is promoted to 12.12% by 6.10%, describes the successful introducing of functional group.
Adopt infrared spectra, Raman, XRD etc. to analyze means of testing to analyze the modified graphene prepared, test result shows, and successfully can obtain modified graphene by this test.
Claims (5)
1. a preparation method for modified graphene, is characterized in that the preparation method of modified graphene carries out according to the following steps:
One, the oxide treatment of graphite: add the vitriol oil that 0.3L ~ 3L massfraction is 98% in the reactor of drying, under the condition stirred, add 10g ~ 100g Graphite Powder 99,0.1L ~ 1L massfraction are the concentrated nitric acid of 65%, ultrasonic 10min ~ 60min, be be incubated 10min ~ 100min under the condition of 20 DEG C ~ 60 DEG C in temperature, filter, the solid distilled water repetitive scrubbing obtained 3 times ~ 5 times, dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtains graphite oxide;
Two, the preparation of benzophenone hydrazone derivative: the benzophenone derivates of 2g ~ 20g is joined in round-bottomed flask, add 50mL ~ 1000mL dehydrated alcohol successively and 1g ~ 50g massfraction is the hydrazine hydrate solution of 85%, to reflux 24h ~ 72h under temperature is 80 DEG C and the condition that stirs, then underpressure distillation goes out the dehydrated alcohol of added dehydrated alcohol volume 40% ~ 60%, remaining reaction solution is crystallisation by cooling 10min ~ 60min in ice-water bath, suction filtration product, the solid distilled water wash obtained 3 times ~ 5 times, be dry 12h ~ 36h under the condition of 20 DEG C ~ 60 DEG C in vacuum and temperature, obtain benzophenone hydrazone derivative,
Three, the preparation of two aryldiazonium methane Derivatives: benzophenone hydrazone derivative 0.1g ~ 5g step 2 obtained is added in the round-bottomed flask that 5mL ~ 200mL tetrahydrofuran (THF) is housed, then add the anhydrous sodium sulphate of 0.1g ~ 10g, the MnO of 0.1g ~ 10g successively
2with the alcohol saturated solution of the KOH of 0.1mL ~ 10mL, 1h ~ 12h is stirred under the condition of room temperature lucifuge, employing sand core funnel filters, with methylene dichloride repetitive scrubbing 3 times ~ 5 times, the filtrate obtained is dry 12h ~ 36h under vacuum and temperature are the condition of 20 DEG C ~ 60 DEG C, obtains two aryldiazonium methane Derivatives;
Four, the preparation of modified graphene: two aryldiazonium methane Derivatives 0.1g ~ 5g step 3 obtained are added in the round-bottomed flask that 10mL ~ 1000mL methylene dichloride is housed, add the graphite oxide that 0.1g ~ 50g step one obtains again, lucifuge underpressure distillation goes out whole solvent, gained solid reacts 10min ~ 120min under temperature is the condition of 100 DEG C ~ 200 DEG C, by washed with dichloromethane 3 ~ 5 times, with distilled water wash 3 ~ 5 times, the solid dispersal obtained in acetone, ultrasonic disperse 1h ~ 6h, suction filtration, the solid obtained is dry 12h ~ 36h under the condition of vacuum and subzero 20 DEG C ~ 60 DEG C, obtain modified graphene.
2. the preparation method of a kind of modified graphene according to claim 1, is characterized in that the benzophenone derivates described in step 2 is benzophenone, 4-phenyl benzophenone or 3,4-dimethyl benzophenone.
3. the preparation method of a kind of modified graphene according to claim 1, it is characterized in that the benzophenone derivates described in step 2 is 4,4'-dimethoxy-benzophenone, 4, two (dimethylamino) benzophenone of 4'-or two (dimethylamino) thiobenzophenon of 4,4'-.
4. the preparation method of a kind of modified graphene according to claim 1, is characterized in that the benzophenone derivates described in step 2 is 4-methyl benzophenone, 4-methoxy benzophenone or 3,4-dimethyl benzophenone.
5. the preparation method of a kind of modified graphene according to claim 1, is characterized in that the benzophenone derivates described in step 2 is two (diethylin) benzophenone of 4,4'-dimethyl benzophenone or 4,4'-.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106400506A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Waterborne polyurethane textile size based on graphene modification and preparation method thereof |
| CN108821272A (en) * | 2018-07-10 | 2018-11-16 | 盐城工学院 | The preparation method of method and its doping corrosion-inhibiting coating based on the covalent modified graphene of Cabbeen |
| CN109715860A (en) * | 2016-09-16 | 2019-05-03 | 曼彻斯特大学 | The production of functionalized graphite's alkene |
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| CN103787307A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Preparation method of modified graphite |
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| CN103787307A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Preparation method of modified graphite |
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| 方瑞萍等: ""碳材料的芳基重氮盐改性及其应用进展"", 《化工新型材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715860A (en) * | 2016-09-16 | 2019-05-03 | 曼彻斯特大学 | The production of functionalized graphite's alkene |
| CN106400506A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Waterborne polyurethane textile size based on graphene modification and preparation method thereof |
| CN108821272A (en) * | 2018-07-10 | 2018-11-16 | 盐城工学院 | The preparation method of method and its doping corrosion-inhibiting coating based on the covalent modified graphene of Cabbeen |
| CN108821272B (en) * | 2018-07-10 | 2020-06-09 | 盐城工学院 | Method for covalent modification of graphene based on carbene and preparation method of doped anticorrosive coating of graphene |
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