CN104843677B - porous graphene and preparation method thereof - Google Patents
porous graphene and preparation method thereof Download PDFInfo
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- CN104843677B CN104843677B CN201510150669.3A CN201510150669A CN104843677B CN 104843677 B CN104843677 B CN 104843677B CN 201510150669 A CN201510150669 A CN 201510150669A CN 104843677 B CN104843677 B CN 104843677B
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- shitosan
- acetic acid
- aqueous acetic
- ultrasonically treated
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 230000006196 deacetylation Effects 0.000 claims description 7
- 238000003381 deacetylation reaction Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 241000446313 Lamella Species 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005087 graphitization Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 229920001661 Chitosan Polymers 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
Abstract
The invention discloses a kind of porous graphene and preparation method thereof.Methods described is：By in the aqueous acetic acid of graphite raw material addition shitosan, using shitosan as remover, by ultrasonically treated, centrifugal purification, the grapheme material with loose structure is prepared for.The grapheme material not only has loose structure, and the number of plies is less, and lamella lateral dimension is larger.Compared with prior art, ultrasonically treated due to only having been used in the present invention, preparation method is simple and easy to apply；Due to using graphite as raw material, the porous graphene material degree of graphitization of preparation is high.The porous graphene material has huge application value in fields such as absorption, catalysis, gas separation and ultracapacitors.
Description
Technical field
The invention belongs to grapheme material technical field, and in particular to a kind of porous graphene and preparation method thereof.
Background technology
The nanoscale graphite material that grapheme material is made up of mono-layer graphite, porous graphene is the lamella in Graphene
In some are manufactured by the method for physics or chemistry there is the hole of nano-scale, loose structure cause Graphene the energy,
Catalysis or sorbing material aspect have very big advantage.
The current preparation on the grapheme material with loose structure mainly has following methods：(1) by the graphite of multilayer
Alkene carries out hydro-thermal reaction with surfactant in strong alkali aqueous solution, but this method is added in stone due to surfactant
Many functional groups are introduced in black alkene lamella；(2) carbon materials such as Graphene and transition metal are heated simultaneously and obtains porous stone
Black alkene, but this method has used expensive transition metal；(3) chemical deposition obtains graphene sheet layer, Ran Houtong
Over etching formation porous graphene, but this method complex process, it is relatively costly；(4) graphite is mixed with nano-metal particle
After conjunction, dissolved by acid treatment and obtain porous graphene material, because the introducing of nano metal improves the cost of reaction.
The content of the invention
It is an object of the invention to overcome deficiencies of the prior art, there is provided porous graphene and its preparation side
Method.The present invention adds graphite raw material in the aqueous acetic acid of shitosan, using shitosan as remover, by ultrasonically treated,
Centrifugal purification, is prepared for the grapheme material with loose structure.
The purpose of the present invention is realized at least through one of following technical scheme.
A kind of porous graphene, its graphene sheet layer thickness is 0.5~2 nanometer, 1~30 micron of lateral dimension；Graphene
Surface holes are uniformly distributed, and aperture is 10 nanometers~500 nanometers.
The method for preparing a kind of above-mentioned porous graphene, step is as follows：A certain amount of shitosan is dissolved in acetic acid water-soluble
In liquid, the aqueous acetic acid of shitosan is obtained；Graphite is added in the aqueous acetic acid of shitosan, stirring must be mixed to well mixed
Close liquid；Mixed liquor is put into ultrasonic cleaning machine, is carried out ultrasonically treated；By the mixed liquor after above-mentioned ultrasound by centrifugal purification,
Obtain the grapheme material with loose structure；The ultrasonically treated temperature is 10~75 DEG C；Ultrasonically treated power is 420
~600W.
Further optimally, the shitosan and the mass ratio of the graphite are 1:10~10:1.
Further optimally, the weight average molecular weight of the shitosan is 5.0 × 103~1.0 × 106。
Further optimally, the deacetylation of the shitosan is 40%~95%.
Further optimally, the volumetric concentration of the aqueous acetic acid is 0.5%~4%.
Further optimally, the mass concentration of the aqueous acetic acid of the shitosan is 0.1~0.5mg/mL.
Further optimally, the ultrasonically treated time is 0.5~24 hour.
Further optimally, the mixed liquor is centrifuged 5~10 minutes by 1000~2000rpm.
Further optimally, the product after centrifugation reuses the aqueous acetic acid that volumetric concentration is 0.5%~4% and carries out
15000~20000rpm eccentric cleanings, the time of eccentric cleaning is 1.5~3 hours.
Compared with prior art, the present invention has advantages below：
Preparation method of the present invention is simple and easy to apply, and raw material is easy to get.By present invention uses work that is ultrasonically treated and being limited
Skill parameter, makes obtained porous graphene material degree of graphitization high, and the thickness of lamella is 0.5~2 nanometer, lamella lateral dimension compared with
Greatly, 1~30 micron, a diameter of 10~500 nanometers of lamella hole.The grapheme material not only has loose structure, and the number of plies
Less, lamella lateral dimension is larger.The method is simple and easy to apply, and cost is relatively low.
Brief description of the drawings
The porous stone that Fig. 1 a~Fig. 1 d are respectively by ultrasonically treated 0.5 hour, 8 hours, 16 hours and obtain for 24 hours
The AFM data of black alkene；
Fig. 1 e are the AFM data and its height of the big size porous Graphene for obtaining for ultrasonically treated 8 hours
Figure；
Fig. 2 a, Fig. 2 b are respectively the x-ray photoelectron power spectrum of graphite and porous graphene of the invention.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but implementation of the invention and protection are not
It is limited to this, is that those skilled in the art can refer to prior art realization if having not describing part in detail especially below.
Embodiment 1：
Dose volume concentration is 0.5% aqueous acetic acid, is 5.0 × 10 by weight average molecular weight3, deacetylation is 40%
Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.1mg/mL chitosan solution, stir；
Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:10；
Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 75 DEG C, the time be 0.5 hour, surpass
The power of sound is 600W.
Solution after above-mentioned ultrasound is carried out after 1000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid
15000rpm eccentric cleanings, the time of centrifugation is 0.5 hour.
Embodiment 2：
Dose volume concentration is 2% aqueous acetic acid, is 2.0 × 10 by weight average molecular weight4, deacetylation is 53%
Shitosan is dissolved in aqueous acetic acid, and it is the chitosan solution of 0.2mg/mL that mass concentration is obtained, and is stirred；
Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:5；
Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 60 DEG C, the time be 2 hours, ultrasound
Power be 540W.
Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid
20000rpm eccentric cleanings, the time of centrifugation is 1 hour.
Embodiment 3：
Dose volume concentration is 4% aqueous acetic acid, is 1.5 × 10 by weight average molecular weight5, deacetylation is 60%
Shitosan is dissolved in aqueous acetic acid, and it is the chitosan solution of 0.5mg/mL that mass concentration is obtained, and is stirred；
Graphite is added in above-mentioned chitosan solution, it is 1 with the mass ratio of graphite to control shitosan:1；
Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 30 DEG C, the time be 8 hours, ultrasound
Power be 480W.
Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 5 minutes using above-mentioned aqueous acetic acid
16000rpm eccentric cleanings, the time of centrifugation is 1.5 hours.
Embodiment 4：
Dose volume concentration is 0.5% aqueous acetic acid, is 4.5 × 10 by weight average molecular weight5, deacetylation is 80%
Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.2mg/mL chitosan solution, stir；
Graphite is added in above-mentioned chitosan solution, it is 5 with the mass ratio of graphite to control shitosan:1；
Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 10 DEG C, the time be 16 hours, ultrasound
Power be 420W.
Solution after above-mentioned ultrasound is carried out after 1000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid
18000rpm eccentric cleanings, the time of centrifugation is 2 hours.
Embodiment 5：
Dose volume concentration is 0.5% aqueous acetic acid, is 1.0 × 10 by weight average molecular weight6, deacetylation is 95%
Shitosan be dissolved in aqueous acetic acid, be obtained mass concentration for 0.2mg/mL chitosan solution, stir；
Graphite is added in above-mentioned chitosan solution, it is 10 with the mass ratio of graphite to control shitosan:1；
Above-mentioned mixed liquor is put into ultrasonic cleaning machine carry out it is ultrasonically treated, temperature be 30 DEG C, the time be 24 hours, ultrasound
Power be 600W.
Solution after above-mentioned ultrasound is carried out after 2000rpm is centrifuged centrifugation in 10 minutes using above-mentioned aqueous acetic acid
15000rpm eccentric cleanings, the time of centrifugation is 3 hours.
Fig. 1 a~Fig. 1 d give the change of the size of the pore structure with the change Graphene of ultrasonic time.Contrast hair
Existing, with the extension of ultrasonic time, pore structure becomes big from small, and size is from 10 nanometers to 500 nanometers.Fig. 1 e are ultrasonically treated 8 small
When the AFM data and its height map of big size porous Graphene that obtain, graphene sheet layer thickness is 0.9 nanometer,
Lateral dimension has reached 30 microns.
Fig. 2 a, Fig. 2 b give the x-ray photoelectron power spectrum of porous graphene, it is recognised that prepared by the present invention from figure
The grapheme material with loose structure oxygen-containing functional group it is less, degree of graphitization is high.
Claims (3)
1. the method for preparing porous graphene, the porous graphene lamellar spacing is 0.5~2 nanometer, and lateral dimension 1~30 is micro-
Rice；Graphenic surface hole is uniformly distributed, and aperture is 10 nanometers~500 nanometers；It is characterized in that preparation process is as follows：Will be a certain amount of
Shitosan be dissolved in aqueous acetic acid, obtain the aqueous acetic acid of shitosan；Added in the aqueous acetic acid of shitosan
Graphite, stirs to well mixed to obtain mixed liquor；Mixed liquor is put into ultrasonic cleaning machine, is carried out ultrasonically treated；By above-mentioned ultrasound
Mixed liquor afterwards obtains the grapheme material with loose structure by centrifugal purification；The ultrasonically treated temperature is 10 ~ 75
℃；Ultrasonically treated power is 420 ~ 600W；The shitosan is 1 with the mass ratio of the graphite:10~10:1；The shell gathers
The weight average molecular weight of sugar is 5.0 × 103~1.0×106；The deacetylation of the shitosan is 40% ~ 95%；The aqueous acetic acid
Volumetric concentration be 0.5% ~ 4%；The mass concentration of the aqueous acetic acid of the shitosan is 0.1 ~ 0.5mg/mL；Ultrasonically treated
Time is 0.5 ~ 24 hour.
2. preparation method according to claim 1, it is characterised in that the mixed liquor is centrifuged 5 by 1000 ~ 2000 rpm
~ 10 minutes.
3. preparation method according to claim 1, it is characterised in that it is 0.5% that the product after centrifugation reuses volumetric concentration
~ 4% aqueous acetic acid carries out 15000 ~ 20000 rpm eccentric cleanings, and the time of eccentric cleaning is 1.5 ~ 3 hours.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510150669.3A CN104843677B (en) | 2015-03-31 | 2015-03-31 | porous graphene and preparation method thereof |
| US15/563,406 US10005957B2 (en) | 2015-03-31 | 2015-12-31 | Porous graphene, graphene quantum dot and green preparation method for porous graphene and graphene quantum dot |
| PCT/CN2015/100021 WO2016155396A1 (en) | 2015-03-31 | 2015-12-31 | Porous graphene, graphene quantum dot, and green manufacturing method therefor |
Applications Claiming Priority (1)
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| CN201510150669.3A CN104843677B (en) | 2015-03-31 | 2015-03-31 | porous graphene and preparation method thereof |
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| CN104843677A CN104843677A (en) | 2015-08-19 |
| CN104843677B true CN104843677B (en) | 2017-06-06 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502352A (en) * | 2015-12-11 | 2016-04-20 | 华南理工大学 | Porous graphene, graphene quantum dot and green preparation method of porous graphene and graphene quantum dot |
| US10005957B2 (en) | 2015-03-31 | 2018-06-26 | South China University Of Technology | Porous graphene, graphene quantum dot and green preparation method for porous graphene and graphene quantum dot |
| CN105523549B (en) * | 2016-01-28 | 2017-10-27 | 成都新柯力化工科技有限公司 | A kind of remover and application that graphene is prepared for mechanical stripping method |
| US10160653B2 (en) | 2016-05-31 | 2018-12-25 | City University Of Hong Kong | Method of producing graphene-based materials, obtainable materials and their use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849734A (en) * | 2012-09-28 | 2013-01-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method of porous graphene |
| CN103738957A (en) * | 2014-01-17 | 2014-04-23 | 上海交通大学 | Graphene surface pore-forming method |
| WO2014154911A1 (en) * | 2012-11-21 | 2014-10-02 | Abengoa Solar New Technologies, S.A. | Method for obtaining solid graphene samples or suspensions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849734A (en) * | 2012-09-28 | 2013-01-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method of porous graphene |
| WO2014154911A1 (en) * | 2012-11-21 | 2014-10-02 | Abengoa Solar New Technologies, S.A. | Method for obtaining solid graphene samples or suspensions |
| CN103738957A (en) * | 2014-01-17 | 2014-04-23 | 上海交通大学 | Graphene surface pore-forming method |
Non-Patent Citations (1)
| Title |
|---|
| 壳聚糖剥离石墨烯及生物传感器的构建;王振兵;《中国学位论文全文数据库》;20131030;正文第24、25、29、35页 * |
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