CN105692593B - A kind of preparation method of porous graphene - Google Patents
A kind of preparation method of porous graphene Download PDFInfo
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- CN105692593B CN105692593B CN201410687076.6A CN201410687076A CN105692593B CN 105692593 B CN105692593 B CN 105692593B CN 201410687076 A CN201410687076 A CN 201410687076A CN 105692593 B CN105692593 B CN 105692593B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention discloses a kind of preparation method of porous graphene, concretely comprises the following steps：1) by graphene dispersion in nmp solution, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；2) graphene dispersing solution is supported in the way of negative pressure leaching on filter membrane and obtains filmy graphite alkene film；3) electrochemical corrosion in electrolyte solution is placed in by electrode of filmy graphite alkene film and obtains porous graphene.Preparation method low cost, convenient, fast, it is not necessary to high temperature, the size in hole is controllable, and obtained porous graphene can carry out subsequent treatment with original position.
Description
Technical field
The present invention relates to field of graphene, and in particular to a kind of preparation method of porous graphene.
Background technology
Graphene (Graphene) be it is a kind of by carbon atom with SP2 hybridized orbits constitute hexangle type be in honeycomb lattice plane
Film, the two-dimensional material of only one of which carbon atom thickness., Univ Manchester UK physicist An Deliehaimu in 2004
With Constantine's Nuo Woxiao loves, graphene is successfully isolated from graphite in an experiment, and confirming it can individually deposit
In, two people also because the initiative experiment in two-dimensional graphene material is served as reasons, Nobel Prize in physics in 2010 is obtained jointly.Graphite
The appearance of alkene causes global research boom.It is can to accomplish single layer of carbon atom two-dimensional arrangements, graphene honeycomb lattice
Normal rigid, in room temperature situation, the speed for transmitting electronics is all faster than known conductor.The atomic-scale structure of graphene is very special
Very, because graphene is substantially a kind of transparent, good conductor, it also is adapted for for manufacturing transparent touch screen, tabula rasa, even
It is that solar cell has significant application value in terms of Semiconductor Physics, catalysis.Grapheme material or a kind of excellent change
Property agent, it is applicable due to its high conductance, high-specific surface area in terms of new energy field such as ultracapacitor, lithium ion battery
In being used as electrode material auxiliary agent.Because graphene has extra-high surface area to mass ratio, graphene can be used for super
The conductive electrode of capacitor.Scientist thinks that the storage energy density of this ultracapacitor can be more than existing capacitor.
But graphene is a kind of two-dimensional material of sheet, during you use graphene, material is often related to
Transmission and diffusion, the diffusion of such as electrolyte, the transmission of carrier, the diffusion of gas.Because two-dimensional sheet material is in superposition
It is unfavorable for material transmission during use, thus has a strong impact on the performance of graphene performance.In addition the electronics in graphene is in layer
Between transmission speed it is fast, but electronics from graphene be injected on materials of electrolyte or other absorption when it is relatively difficult.
The content of the invention
The problem of present invention exists for prior art passes through electrochemistry there is provided a kind of preparation method of porous graphene
Method carries out electrochemical corrosion to graphene, and graphene is corroded using the anodic oxidation in electrochemical process, and cathode hydrogen evolution,
Corrosion pore-creating is carried out to graphene in the electrolytic solution, so that porous graphene is made, and the size of hole can be 0.2nm-
300nm, these holes provide effective passage for the transmission of material (liquid, gaseous state), thus can greatly improve graphene
Performance, preparation method low cost, convenient, fast, it is not necessary to high temperature, not only the size in hole is controllable, porous graphene
Shape it is also controllable, and obtained porous graphene can with original position carry out subsequent treatment.
The technical solution adopted by the present invention is：
A kind of preparation method of porous graphene, is concretely comprised the following steps：
1) by graphene dispersion in nmp solution, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) graphene dispersing solution is supported in the way of negative pressure leaching on filter membrane and obtains filmy graphite alkene；
3) electrochemical corrosion in electrolyte solution is placed in by electrode of filmy graphite alkene and obtains porous graphene.
Described preparation method, in addition to step 4) porous graphene is dispersed in nmp solution, obtain scattered sheet many
Hole graphene.
The step 3) in, positive source is connect by electrode of filmy graphite alkene, anodic attack is carried out.
The step 3) in, power cathode is connect by electrode of filmy graphite alkene, cathodic corrosion is carried out.
The step 1) in graphene dispersing solution mass concentration be 2mg/ml-10mg/ml.
The step 2) in filter membrane be PP filter membranes, or PTFE filter membranes, a diameter of 27mm-100mm of the filter membrane.
The step 3) in electrochemical corrosion voltage be 1-10v.
The step 3) in electrochemical corrosion time be 15min-180min..
The step 3) in electrolyte solution be dilute sulfuric acid, NaOH or CH3COOH。
The present invention also provides a kind of porous graphene prepared through above-mentioned preparation method answering on as Substrates
With.
The invention has the advantages that：
The present invention corrodes pore-creating to graphene in the electrolytic solution in the method for electrochemical corrosion.The advantage of this method is
Low cost, convenient, fast, it is not necessary to high temperature, the size in hole is controllable, after obtained porous graphene can be carried out with original position
Continuous processing.
The porous graphene that the present invention is prepared still remains two-dimension plane structure, but has very on two dimensional surface
Multiple hole, these holes provide effective passage for the transmission of material, thus can greatly improve the performance of graphene.This
Outside, the carbon atom of hole edge is conducive to carrier to be transmitted between graphene and graphene ambient substance.Hole after tested
Size is 0.2nm-300nm.This method can also realize the rule corruption of microcosmic graphene by special mechanism using nano-electrode
Erosion, obtains desired pattern.
Brief description of the drawings
Fig. 1 is the transmission electron microscope figure of porous graphene prepared by embodiment 1.
Fig. 2 be embodiment 1 in step 1) in graphene raw material transmission electron microscope figure.
Fig. 3 is the transmission electron microscope figure of porous graphene prepared by embodiment 2.
Fig. 4 is that the porous graphene of application examples 3 supports MnO2The TEM test charts of nano particle.
Embodiment
Embodiment 1, a kind of preparation of porous graphene
Concretely comprise the following steps：
1) using graphene as raw material, by 0.2g graphene dispersion in 100ml nmp solution, sonic oscillation is scattered equal
It is even to obtain graphene dispersing solution；
2) 10ml graphene dispersing solution is taken to be supported on a diameter of 50mm tetrafluoroethene filter membrane in the way of negative pressure leaching
On, obtain filmy graphite alkene；
3) positive source is connect from as electrode with filmy graphite alkene, is that platinum electrode connects power cathode to electrode, dilute
To be carried out under 1.5v voltages after electrochemical corrosion 90min in the electrolyte solution of sulfuric acid, porous graphene is obtained；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous graphene.
Scattered flake porous graphene is done into TEM signs, as a result as shown in figure 1, can clearly be seen in piece in figure
With the presence of many polygonal holes on the graphene of shape.Fig. 2 be embodiment 1 in step 1) in graphene raw material transmission electricity
Sub- microscope figure.Contrast Fig. 1 and 2, it can be seen that there is substantial amounts of hole by the graphenic surface after electrochemical corrosion.And
It is several nanometers to tens nanometers that the size distribution ranges of hole, which can be found out,.
Embodiment 2, a kind of preparation of porous graphene
Concretely comprise the following steps：
1) using graphene as raw material, by 0.8g graphene dispersion in 100ml nmp solution, sonic oscillation is scattered equal
It is even to obtain graphene dispersing solution；
2) take 10ml graphene dispersing solution to be supported in the way of negative pressure leaching on a diameter of 90mm PP filter membranes, obtain thin
Membranaceous graphene；
3) power cathode is connect from as electrode with filmy graphite alkene, is that platinum electrode connects positive source to electrode,
CH3To be carried out under 3.5v voltages after electrochemical corrosion 180min in COOH electrolyte solution, porous graphene is obtained；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous graphene.
Scattered flake porous graphene film is done into TEM signs, the porous stone of the preparation of embodiment 2 is as a result illustrated in figure 3
Can clearly be seen in the transmission electron microscope figure of black alkene, figure has many polygonal holes to deposit on the graphene of sheet
.And can find out that the size distribution ranges of hole are maximum to hundreds of nanometers.
Embodiment 3, a kind of preparation of porous graphene
Concretely comprise the following steps：
1) using graphene as raw material, by 0.5g graphene dispersion in 100ml nmp solution, sonic oscillation is scattered equal
It is even to obtain graphene dispersing solution；
2) take 10ml graphene dispersing solution to be supported in the way of negative pressure leaching on a diameter of 80mm PP filter membranes, obtain thin
Membranaceous graphene；
3) power cathode is connect from as electrode with filmy graphite alkene, is platinum electrode to electrode, in the electrolysis of dilute sulfuric acid
Carried out in matter solution under 10v voltages after electrochemical corrosion 130min, obtain porous graphene；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous graphene.
Embodiment 4, a kind of preparation of porous graphene
1) using graphene as raw material, by 1.0g graphene dispersion in 100ml nmp solution, sonic oscillation is scattered equal
It is even to obtain graphene dispersing solution；
2) take 10ml graphene dispersing solution to be supported in the way of negative pressure leaching on a diameter of 50mm PTFE filter membranes, obtain
Filmy graphite alkene；
3) positive source is connect from as electrode with filmy graphite alkene, is platinum electrode to electrode, in dilute NaOH electrolysis
Carried out in matter solution under 10v voltages after electrochemical corrosion 180min, obtain porous graphene；
4) porous graphene is dispersed in nmp solution, scattered flake porous graphene.
Application examples 1, a kind of porous graphene are being used as the application supported on Ag nano-particle materials
The flake porous graphene deionized water rinsing that will be prepared in implementation 1, is then transferred into concentration for (0.001M)
AgNO3(0.01M) NaNO3In mixed solution, constant current electro-deposition Ag nano particles, porous graphene connection power cathode.By
The porous graphene material that porous graphite obtains Ag loads is taken out after 30 seconds.Tested by TEM, it can be seen that porous graphene piece
On with the presence of Ag particles.
Application examples 2, a kind of porous graphene are being used as the application supported on bismuth tungstate material.
By after the flake porous graphene deionized water rinsing prepared in embodiment 1 and 0.02mol bismuth nitrates,
0.01mol ammonium tungstates are mixed in 75ml water, and mixed liquor is put into autoclave after stirring, by 200 degree ten hours
After reaction, mixed liquor is filtered and obtains the porous graphene material for supporting bismuth tungstate.Tested by TEM, it can be seen that porous stone
With the presence of particle on black alkene piece.Tested through XRD, contain Bi in gained sample2WO6Composition, it is inferred that being supported on porous graphene
Material on piece is Bi2WO6。
Application examples 3, a kind of porous graphene are as supporting MnO2Application on nano-particle material
The flake porous graphene deionized water rinsing that will be prepared in implementation 1, is then transferred into concentration for (0.001M)
In acetic acid manganese solution, DC voltage-stabilizing electro-deposition MnO2Nano particle, porous graphene connection power cathode.Taken after 10 minutes
Go out porous graphene.Tested by TEM, TEM results as shown in fig. 4, it can be seen that with the presence of a large amount of particles on porous graphene,
Understand MnO2Nano particle is successfully supported on porous graphene.
Claims (10)
1. a kind of preparation method of porous graphene, it is characterised in that concretely comprise the following steps：
1) by graphene dispersion in nmp solution, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) graphene dispersing solution is supported in the way of negative pressure leaching on filter membrane and obtains filmy graphite alkene；
3) electrochemical corrosion in electrolyte solution is placed in by electrode of filmy graphite alkene and obtains porous graphene.
2. preparation method according to claim 1, it is characterised in that also including step 4) porous graphene is dispersed in
In nmp solution, scattered flake porous graphene is obtained.
3. preparation method according to claim 1, it is characterised in that the step 3) in, using filmy graphite alkene as electricity
Pole connects positive source, carries out anodic attack.
4. preparation method according to claim 1, it is characterised in that the step 3) in, using filmy graphite alkene as electricity
Pole connects power cathode, carries out cathodic corrosion.
5. preparation method according to claim 1, it is characterised in that the step 1) in graphene dispersing solution quality it is dense
Spend for 2mg/ml-10mg/ml.
6. preparation method according to claim 1, it is characterised in that the step 2) in filter membrane be tetrafluoroethene filter
Film, PP filter membranes, a diameter of 27mm-100mm of the filter membrane.
7. preparation method according to claim 1, it is characterised in that the step 3) in the voltage of electrochemical corrosion be 1-
10V。
8. preparation method according to claim 1, it is characterised in that the step 3) in time of electrochemical corrosion be
15min-180min。
9. preparation method according to claim 1, it is characterised in that the step 3) in electrolyte solution be dilute sulfuric acid,
NaOH or CH3COOH。
10. the porous graphene that a kind of preparation method as described in claim any one of 1-9 is prepared is as Substrates
On application.
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| CN106517993B (en) * | 2016-10-18 | 2018-12-18 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene/montmorillonite Composite porous membrane and preparation method thereof |
| CN106517333B (en) * | 2016-11-01 | 2017-08-29 | 中南大学 | A kind of compliant conductive MoS2Insulation film and preparation method thereof |
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| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103145120A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Preparation method of porous graphene |
| CN103466603A (en) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene dispersion liquid, and preparation method of graphene film |
| CN103466604A (en) * | 2013-08-13 | 2013-12-25 | 华东理工大学 | Preparation method of porous graphene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103145120A (en) * | 2013-03-19 | 2013-06-12 | 苏州格瑞丰纳米科技有限公司 | Preparation method of porous graphene |
| CN103466603A (en) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene dispersion liquid, and preparation method of graphene film |
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