CN104843677A - Porous graphene and preparation method therefor - Google Patents
Porous graphene and preparation method therefor Download PDFInfo
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- CN104843677A CN104843677A CN201510150669.3A CN201510150669A CN104843677A CN 104843677 A CN104843677 A CN 104843677A CN 201510150669 A CN201510150669 A CN 201510150669A CN 104843677 A CN104843677 A CN 104843677A
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- chitosan
- acetic acid
- aqueous acetic
- porous graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229920001661 Chitosan Polymers 0.000 claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 13
- 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
- 239000000203 mixture Substances 0.000 claims description 2
- 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
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 241000446313 Lamella Species 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 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 present invention discloses porous graphene and a preparation method therefor. The preparation method comprises the following steps: adding a graphite raw material into an acetic acid solution of chitosan; and by taking chitosan as a peeling agent, carrying out ultrasonic treatment and centrifugal purification to prepare the porous graphene material. The graphene material not only has a porous structure, but also is relatively few in number of layers, and the transverse size of the flaky layer is relatively large. Compared to the prior art, as only ultrasonic treatment is carried out, the preparation method is simple and easy to implement; as the graphite is taken as the raw material, the prepared porous graphene material is high in degree of graphitization. The porous graphene material has a huge application value in the fields of absorption, catalysis, gas separation, super capacitors and the like.
Description
Technical field
The invention belongs to grapheme material technical field, be specifically related 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 manufactures by the method for physics or chemistry the hole that some have nano-scale in the lamella of Graphene, and vesicular structure makes Graphene have very large advantage in the energy, catalysis or sorbing material.
Preparation at present about the grapheme material with vesicular structure mainly contains following methods: the Graphene of multilayer and tensio-active agent are carried out hydro-thermal reaction by (1) in strong alkali aqueous solution, but this method introduces a lot of functional groups due to being added in graphene sheet layer of tensio-active agent; (2) carbon materials such as Graphene and transition metal are heated simultaneously obtain porous graphene, but this method employs expensive transition metal; (3) chemical deposition obtains graphene sheet layer, then forms porous graphene by etching, but this method complex process, and cost is higher; (4), after being mixed with nano-metal particle by graphite, dissolved by acid treatment and obtain porous graphene material, the introducing due to nano metal improves the cost of reaction.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, porous graphene and preparation method thereof is provided.Graphite raw material adds in the aqueous acetic acid of chitosan by the present invention, and using chitosan as stripper, through supersound process, centrifugal purification, has prepared the grapheme material with vesicular structure.
Object of the present invention realizes one of at least by the following technical programs.
A kind of porous graphene, its graphene film layer thickness is 0.5 ~ 2 nanometer, lateral dimension 1 ~ 30 micron; Graphenic surface hole is uniformly distributed, and aperture is 10 nanometer ~ 500 nanometers.
Prepare the method for above-mentioned a kind of porous graphene, step is as follows: be dissolved in aqueous acetic acid by a certain amount of chitosan, obtains the aqueous acetic acid of chitosan; In the aqueous acetic acid of chitosan, add graphite, be stirred to and mix to obtain mixed solution; Mixed solution is put into ultrasonic cleaning machine, carries out supersound process; By above-mentioned ultrasonic after mixed solution through centrifugal purification, obtain the grapheme material with vesicular structure; The temperature of described supersound process is 10 ~ 75 DEG C; The power of supersound process is 420 ~ 600W.
Further optimally, the mass ratio of described chitosan and described graphite is 1:10 ~ 10:1.
Further optimally, the weight-average molecular weight of described chitosan is 5.0 × 10
3~ 1.0 × 10
6.
Further optimally, the deacetylation of described chitosan is 40% ~ 95%.
Further optimally, the volumetric concentration of described aqueous acetic acid is 0.5% ~ 4%.
Further optimally, the mass concentration of the aqueous acetic acid of described chitosan is 0.1 ~ 0.5mg/mL.
Further optimally, the time of described supersound process is 0.5 ~ 24 hour.
Further optimally, described mixed solution through 1000 ~ 2000rpm centrifugal 5 ~ 10 minutes.
Further optimally, the product after centrifugal re-use volumetric concentration be 0.5% ~ 4% aqueous acetic acid carry out 15000 ~ 20000rpm eccentric cleaning, the time of eccentric cleaning is 1.5 ~ 3 hours.
Compared with prior art, the present invention has the following advantages:
Preparation method of the present invention is simple, and raw material is easy to get.Due to the processing parameter that present invention uses supersound process and limit, make the porous graphene material degree of graphitization that obtains high, the thickness of lamella is 0.5 ~ 2 nanometer, and lamella lateral dimension is comparatively large, and 1 ~ 30 micron, the diameter in lamella hole is 10 ~ 500 nanometers.This grapheme material not only has vesicular structure, and the number of plies is less, and lamella lateral dimension is larger.The method is simple, and cost is lower.
Accompanying drawing explanation
Fig. 1 a ~ Fig. 1 d is respectively through supersound process 0.5 hour, 8 hours, 16 hours and the AFM data of porous graphene that obtains for 24 hours;
Fig. 1 e is AFM data and the height map thereof of the big size porous Graphene that supersound process obtains for 8 hours;
Fig. 2 a, Fig. 2 b are respectively the x-ray photoelectron power spectrum of graphite and porous graphene of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but enforcement of the present invention and protection are not limited thereto, and do not describe part in detail especially if having below, is all that those skilled in the art can refer to existing techniques in realizing.
Embodiment 1:
Dose volume concentration is the aqueous acetic acid of 0.5%, is 5.0 × 10 by weight-average molecular weight
3, deacetylation be 40% chitosan be dissolved in aqueous acetic acid, obtained mass concentration is the chitosan solution of 0.1mg/mL, stirs;
Joined by graphite in above-mentioned chitosan solution, the mass ratio controlling chitosan and graphite is 1:10;
Above-mentioned mixed solution is put into ultrasonic cleaning machine and carries out supersound process, temperature is 75 DEG C, and the time is 0.5 hour, and ultrasonic power is 600W.
By above-mentioned ultrasonic after solution after centrifugal 10 minutes of 1000rpm is centrifugal, use above-mentioned aqueous acetic acid to carry out 15000rpm eccentric cleaning, the centrifugal time is 0.5 hour.
Embodiment 2:
Dose volume concentration is the aqueous acetic acid of 2%, is 2.0 × 10 by weight-average molecular weight
4, deacetylation be 53% chitosan be dissolved in aqueous acetic acid, obtained mass concentration is the chitosan solution of 0.2mg/mL, stirs;
Joined by graphite in above-mentioned chitosan solution, the mass ratio controlling chitosan and graphite is 1:5;
Above-mentioned mixed solution is put into ultrasonic cleaning machine and carries out supersound process, temperature is 60 DEG C, and the time is 2 hours, and ultrasonic power is 540W.
By above-mentioned ultrasonic after solution after centrifugal 10 minutes of 2000rpm is centrifugal, use above-mentioned aqueous acetic acid to carry out 20000rpm eccentric cleaning, the centrifugal time is 1 hour.
Embodiment 3:
Dose volume concentration is the aqueous acetic acid of 4%, is 1.5 × 10 by weight-average molecular weight
5, deacetylation be 60% chitosan be dissolved in aqueous acetic acid, obtained mass concentration is the chitosan solution of 0.5mg/mL, stirs;
Joined by graphite in above-mentioned chitosan solution, the mass ratio controlling chitosan and graphite is 1:1;
Above-mentioned mixed solution is put into ultrasonic cleaning machine and carries out supersound process, temperature is 30 DEG C, and the time is 8 hours, and ultrasonic power is 480W.
By above-mentioned ultrasonic after solution after centrifugal 5 minutes of 2000rpm is centrifugal, use above-mentioned aqueous acetic acid to carry out 16000rpm eccentric cleaning, the centrifugal time is 1.5 hours.
Embodiment 4:
Dose volume concentration is the aqueous acetic acid of 0.5%, is 4.5 × 10 by weight-average molecular weight
5, deacetylation be 80% chitosan be dissolved in aqueous acetic acid, obtained mass concentration is the chitosan solution of 0.2mg/mL, stirs;
Joined by graphite in above-mentioned chitosan solution, the mass ratio controlling chitosan and graphite is 5:1;
Above-mentioned mixed solution is put into ultrasonic cleaning machine and carries out supersound process, temperature is 10 DEG C, and the time is 16 hours, and ultrasonic power is 420W.
By above-mentioned ultrasonic after solution after centrifugal 10 minutes of 1000rpm is centrifugal, use above-mentioned aqueous acetic acid to carry out 18000rpm eccentric cleaning, the centrifugal time is 2 hours.
Embodiment 5:
Dose volume concentration is the aqueous acetic acid of 0.5%, is 1.0 × 10 by weight-average molecular weight
6, deacetylation be 95% chitosan be dissolved in aqueous acetic acid, obtained mass concentration is the chitosan solution of 0.2mg/mL, stirs;
Joined by graphite in above-mentioned chitosan solution, the mass ratio controlling chitosan and graphite is 10:1;
Above-mentioned mixed solution is put into ultrasonic cleaning machine and carries out supersound process, temperature is 30 DEG C, and the time is 24 hours, and ultrasonic power is 600W.
By above-mentioned ultrasonic after solution after centrifugal 10 minutes of 2000rpm is centrifugal, use above-mentioned aqueous acetic acid to carry out 15000rpm eccentric cleaning, the centrifugal time is 3 hours.
Fig. 1 a ~ Fig. 1 d gives the change of the size of the pore structure of the change Graphene along with ultrasonic time.Contrast finds, along with the prolongation of ultrasonic time, pore structure is large from little change, and size is from 10 nanometers to 500 nanometers.Fig. 1 e is AFM data and the height map thereof of the big size porous Graphene that supersound process obtains for 8 hours, and graphene film layer thickness is 0.9 nanometer, and lateral dimension reaches 30 microns.
Fig. 2 a, Fig. 2 b give the x-ray photoelectron power spectrum of porous graphene, can know from figure, and the oxygen-containing functional group of prepared by the present invention the have grapheme material of vesicular structure is less, and degree of graphitization is high.
Claims (10)
1. a porous graphene, is characterized in that: graphene film layer thickness is 0.5 ~ 2 nanometer, lateral dimension 1 ~ 30 micron; Graphenic surface hole is uniformly distributed, and aperture is 10 nanometer ~ 500 nanometers.
2. prepare the method for a kind of porous graphene described in claim, it is characterized in that step is as follows: a certain amount of chitosan is dissolved in aqueous acetic acid, obtain the aqueous acetic acid of chitosan; In the aqueous acetic acid of chitosan, add graphite, be stirred to and mix to obtain mixed solution; Mixed solution is put into ultrasonic cleaning machine, carries out supersound process; By above-mentioned ultrasonic after mixed solution through centrifugal purification, obtain the grapheme material with vesicular structure; The temperature of described supersound process is 10 ~ 75 DEG C; The power of supersound process is 420 ~ 600W.
3. preparation method according to claim 2, is characterized in that, the mass ratio of described chitosan and described graphite is 1:10 ~ 10:1.
4. preparation method according to claim 2, is characterized in that, the weight-average molecular weight of described chitosan is 5.0 × 10
3~ 1.0 × 10
6.
5. preparation method according to claim 2, is characterized in that, the deacetylation of described chitosan is 40% ~ 95%.
6. preparation method according to claim 2, is characterized in that, the volumetric concentration of described aqueous acetic acid is 0.5% ~ 4%.
7. preparation method according to claim 2, is characterized in that, the mass concentration of the aqueous acetic acid of described chitosan is 0.1 ~ 0.5mg/mL.
8. preparation method according to claim 2, is characterized in that, the time of supersound process is 0.5 ~ 24 hour.
9. preparation method according to claim 2, is characterized in that, described mixed solution centrifugal 5 ~ 10 minutes through 1000 ~ 2000 rpm.
10. preparation method according to claim 2, is characterized in that, the product after centrifugal re-use volumetric concentration be 0.5% ~ 4% aqueous acetic acid carry out 15000 ~ 20000 rpm eccentric cleaning, 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 |
| PCT/CN2015/100021 WO2016155396A1 (en) | 2015-03-31 | 2015-12-31 | Porous graphene, graphene quantum dot, and green manufacturing method therefor |
| 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 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510150669.3A CN104843677B (en) | 2015-03-31 | 2015-03-31 | porous graphene and preparation method thereof |
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| Publication Number | Publication Date |
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| CN104843677A true CN104843677A (en) | 2015-08-19 |
| CN104843677B CN104843677B (en) | 2017-06-06 |
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Cited By (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 |
| CN105523549A (en) * | 2016-01-28 | 2016-04-27 | 成都新柯力化工科技有限公司 | Stripping agent for preparation of graphene with mechanical striping method as well as application |
| WO2016155396A1 (en) * | 2015-03-31 | 2016-10-06 | 华南理工大学 | Porous graphene, graphene quantum dot, and green manufacturing method therefor |
| 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 |
-
2015
- 2015-03-31 CN CN201510150669.3A patent/CN104843677B/en not_active Expired - Fee Related
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 |
|---|
| 王振兵: "壳聚糖剥离石墨烯及生物传感器的构建", 《中国学位论文全文数据库》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016155396A1 (en) * | 2015-03-31 | 2016-10-06 | 华南理工大学 | Porous graphene, graphene quantum dot, and green manufacturing method therefor |
| 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 |
| 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 |
| CN105523549A (en) * | 2016-01-28 | 2016-04-27 | 成都新柯力化工科技有限公司 | Stripping agent for preparation of graphene with mechanical striping method as well as application |
| US10160653B2 (en) | 2016-05-31 | 2018-12-25 | City University Of Hong Kong | Method of producing graphene-based materials, obtainable materials and their use |
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| CN104843677B (en) | 2017-06-06 |
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