CN105692593A - Preparation method for porous graphene - Google Patents
Preparation method for porous graphene Download PDFInfo
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- CN105692593A CN105692593A CN201410687076.6A CN201410687076A CN105692593A CN 105692593 A CN105692593 A CN 105692593A CN 201410687076 A CN201410687076 A CN 201410687076A CN 105692593 A CN105692593 A CN 105692593A
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Abstract
The invention discloses a preparation method for porous graphene. The preparation method comprises the following concrete steps: 1) dispersing graphene in an NMP solution and carrying out ultrasonic vibration for uniform dispersion so as to obtain graphene dispersion liquid; 2) loading the graphene dispersion liquid on a filter membrane in a negative-pressure pumping filtration manner so as to obtain a graphene film; and 3) with the graphene film as an electrode, placing the electrode in an electrolyte solution for electrochemical corrosion so as to obtain porous graphene. The preparation method is low in cost, convenient and fast and does not need high temperature; the pore size of the porous graphene is controllable; and the obtained porous graphene can be subjected to subsequent treatment in situ.
Description
Technical field
The present invention relates to field of graphene, the preparation method being specifically related to a kind of porous graphene。
Background technology
Graphene (Graphene) is a kind of to be formed the flat film that hexangle type is honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness by carbon atom with SP2 hybrid orbital。2004, Univ Manchester UK physicist An Deliehaimu and Constantine's Nuo Woxiao love, from graphite, successfully isolate Graphene in an experiment, and confirm that it can individualism, two people also serve as reasons because of the initiative experiment at two-dimensional graphene material, common acquisition Nobel Prize in physics in 2010。The appearance of Graphene causes global research boom。It is to accomplish monolayer carbon atom two-dimensional arrangements, the normal rigid of Graphene honeycomb lattice, and in room temperature situation, the speed of transmission electronics is all faster than known conductor。The atomic-scale structure of Graphene is very special, due to Graphene substantially a kind of transparent, good conductor, also is adapted for for manufacturing transparent touch screen, tabula rasa or even solaode in Semiconductor Physics, and the aspect such as catalysis has significant application value。Grapheme material or a kind of excellent modifying agent, in new energy field such as ultracapacitor, lithium ion battery, due to its high conductance, high-specific surface area, be applicable to as electrode material auxiliary agent。Owing to Graphene has extra-high surface area to mass ratio, Graphene may be used for the conductive electrode of ultracapacitor。Scientist thinks that the storage energy density of this ultracapacitor can more than existing capacitor。
But Graphene is the two-dimensional material of a kind of lamellar, uses in the process of Graphene at you, often relate to transmission and the diffusion of material, for instance electrolytical diffusion, the transmission of carrier, the diffusion of gas。Because two-dimensional sheet material is unfavorable for that material transmits in superposition use procedure, thus has a strong impact on the performance of Graphene performance。In addition the electronics in Graphene is fast in interlayer transmission speed, but electronics from Graphene be injected into the material of electrolyte or other absorption time relatively difficult。
Summary of the invention
The present invention is directed to prior art Problems existing, the preparation method that a kind of porous graphene is provided, by electrochemical method, Graphene is carried out electrochemical corrosion, utilize the anodic oxidation in electrochemical process, and cathode hydrogen evolution corrodes Graphene, in the electrolytic solution Graphene is carried out corrosion pore-creating, thus preparing porous graphene, and the size of hole can be 0.2nm-300nm, these holes are material (liquid, gaseous state) transmission provide effective passage, thus the performance of Graphene can be greatly improved, this preparation method low cost, convenient, fast, do not need high temperature, not only the size in hole is controlled, the shape of porous graphene is also controlled, and the porous graphene obtained original position can also carry out subsequent treatment。
The technical solution used in the present invention is:
The preparation method of a kind 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 obtained filmy graphite alkene by load in the way of negative pressure leaching on filter membrane；
3) it is placed in electrolyte solution electrochemical corrosion with filmy graphite alkene for electrode and obtains porous graphene。
Described preparation method, also includes step 4) porous graphene is dispersed in nmp solution, obtain scattered flake porous Graphene。
Described step 3) in, connect positive source with filmy graphite alkene for electrode, carry out anodic attack。
Described step 3) in, connect power cathode with filmy graphite alkene for electrode, carry out cathodic corrosion。
Described step 1) in the mass concentration of graphene dispersing solution be 2mg/ml-10mg/ml。
Described step 2) in filter membrane be PP filter membrane, or PTFE filter membrane, the diameter of described filter membrane is 27mm-100mm。
Described step 3) in the voltage of electrochemical corrosion be 1-10v。
Described step 3) in time of electrochemical corrosion be 15min-180min。。
Described step 3) in electrolyte solution be dilute sulfuric acid, NaOH or CH3COOH。
The present invention also provides for a kind of porous graphene prepared through above-mentioned preparation method as the application on Substrates。
The method have the advantages that
Graphene, with the method for electrochemical corrosion, is corroded pore-creating by the present invention in the electrolytic solution。The advantage of this method is low cost, and convenient, fast, it is not necessary to high temperature, the size in hole is controlled, and the porous graphene obtained original position can also carry out subsequent treatment。
The porous graphene that the present invention prepares still remains two-dimension plane structure, but has a lot of hole on two dimensional surface, and the transmission that these holes are material provides effective passage, thus can be greatly improved the performance of Graphene。Additionally, the carbon atom of hole edge is conducive to carrier to transmit between Graphene and Graphene ambient substance。Hole is of a size of 0.2nm-300nm after tested。The method utilizes nano-electrode to realize the rule corrosion of microcosmic Graphene also by special mechanism, it is thus achieved that the pattern wanted。
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure of the porous graphene of embodiment 1 preparation。
Fig. 2 is step 1 in embodiment 1) in the transmission electron microscope figure of Graphene raw material。
Fig. 3 is the transmission electron microscope figure of the porous graphene of embodiment 2 preparation。
Fig. 4 is that application examples 3 porous graphene supports MnO2The TEM test figure of nano-particle。
Detailed description of the invention
Embodiment 1, a kind of porous graphene preparation
Concretely comprise the following steps:
1) with Graphene for raw material, by the graphene dispersion of 0.2g in the nmp solution of 100ml, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) take the graphene dispersing solution of 10ml with the mode load of negative pressure leaching diameter be 50mm tetrafluoroethene filter membrane on, obtain filmy graphite alkene；
3) with filmy graphite alkene from as electrode, connecing positive source, be that platinum electrode connects power cathode to electrode, after carrying out electrochemical corrosion 90min under 1.5v voltage, to obtain porous graphene in the electrolyte solution of dilute sulfuric acid；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous Graphene。
Scattered flake porous Graphene being TEM characterize, result is as it is shown in figure 1, can see clearly in figure and have a lot of polygonal hole to exist on the Graphene of lamellar。Fig. 2 is step 1 in embodiment 1) in the transmission electron microscope figure of Graphene raw material。Contrast Fig. 1 and 2, it can be seen that the graphenic surface after electrochemical corrosion has substantial amounts of hole。And can find out that the size distribution ranges of hole is several nanometers to tens nanometers。
Embodiment 2, a kind of porous graphene preparation
Concretely comprise the following steps:
1) with Graphene for raw material, by the graphene dispersion of 0.8g in the nmp solution of 100ml, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) take the graphene dispersing solution of 10ml with the mode load of negative pressure leaching diameter be 90mm PP filter membrane on, obtain filmy graphite alkene；
3) with filmy graphite alkene from as electrode, connecing power cathode, be that platinum electrode connects positive source to electrode, at CH3, after carrying out electrochemical corrosion 180min under 3.5v voltage, to obtain porous graphene in the electrolyte solution of COOH；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous Graphene。
Scattered flake porous graphene film being TEM characterize, result is illustrated in figure 3 in transmission electron microscope figure, the figure of the porous graphene of embodiment 2 preparation can see have a lot of polygonal hole to exist on the Graphene of lamellar clearly。And can find out that the size distribution ranges of hole is maximum to hundreds of nanometers。
Embodiment 3, a kind of porous graphene preparation
Concretely comprise the following steps:
1) with Graphene for raw material, by the graphene dispersion of 0.5g in the nmp solution of 100ml, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) take the graphene dispersing solution of 10ml with the mode load of negative pressure leaching diameter be 80mm PP filter membrane on, obtain filmy graphite alkene；
3) with filmy graphite alkene from as electrode, connecing power cathode, be platinum electrode to electrode, after carrying out electrochemical corrosion 130min under 10v voltage in the electrolyte solution of dilute sulfuric acid, obtain porous graphene；
4) porous graphene is dispersed in nmp solution, regains scattered flake porous Graphene。
Embodiment 4, a kind of porous graphene preparation
1) with Graphene for raw material, by the graphene dispersion of 1.0g in the nmp solution of 100ml, sonic oscillation is uniformly dispersed to obtain graphene dispersing solution；
2) take the graphene dispersing solution of 10ml with the mode load of negative pressure leaching diameter be 50mm PTFE filter membrane on, obtain filmy graphite alkene；
3) with filmy graphite alkene from as electrode, connecing positive source, be platinum electrode to electrode, after carrying out electrochemical corrosion 180min under 10v voltage in the electrolyte solution of rare NaOH, obtain porous graphene；
4) porous graphene is dispersed in nmp solution, scattered flake porous Graphene。
Application examples 1, a kind of porous graphene are as the application supported on Ag nano-particle material
The flake porous Graphene deionized water rinsing of preparation in 1 will be implemented, be then transferred into concentration for (0.001M) AgNO3(0.01M) NaNO3In mixed solution, Constant Electric Current deposition Ag nano-particle, porous graphene connects power cathode。After 30 seconds, take out porous graphite obtain the porous graphene material of Ag load。Test through TEM, it can be seen that porous graphene sheet has Ag granule exist。
Application examples 2, a kind of porous graphene are as the application supported on bismuth tungstate material。
To mix in 75ml water with 0.02mol bismuth nitrate, 0.01mol ammonium tungstate after the flake porous Graphene deionized water rinsing of preparation in embodiment 1, after stirring, mixed liquor is put in autoclave, after 200 degree of reactions of ten hours, mixed liquor is filtered and obtains the porous graphene material supporting bismuth tungstate。Test through TEM, it can be seen that porous graphene sheet has granule to exist。Test through XRD, containing Bi in gained sample2WO6Composition, therefore conclude that the material that load is on porous graphene sheet is Bi2WO6。
Application examples 3, a kind of porous graphene are as supporting MnO2Application on nano-particle material
To implement the flake porous Graphene deionized water rinsing of preparation in 1, being then transferred into concentration is in (0.001M) manganese acetate solution, DC voltage-stabilizing electro-deposition MnO2Nano-particle, porous graphene connects power cathode。Porous graphene is taken out after 10 minutes。Testing through TEM, TEM result is as shown in fig. 4, it can be seen that there is a large amount of granule to exist on porous graphene, it is known that MnO2Nano-particle is successfully supported on porous graphene。
Claims (10)
1. the preparation method of a 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 obtained filmy graphite alkene by load in the way of negative pressure leaching on filter membrane；
3) it is placed in electrolyte solution electrochemical corrosion with filmy graphite alkene for electrode and obtains porous graphene。
2. preparation method according to claim 1, it is characterised in that also include step 4) porous graphene is dispersed in nmp solution, obtain scattered flake porous Graphene。
3. preparation method according to claim 1, it is characterised in that described step 3) in, connect positive source with filmy graphite alkene for electrode, carry out anodic attack。
4. preparation method according to claim 1, it is characterised in that described step 3) in, connect power cathode with filmy graphite alkene for electrode, carry out cathodic corrosion。
5. preparation method according to claim 1, it is characterised in that described step 1) in the mass concentration of graphene dispersing solution be 2mg/ml-10mg/ml。
6. preparation method according to claim 1, it is characterised in that described step 2) in filter membrane be tetrafluoroethene filter membrane, PP filter membrane, the diameter of described filter membrane is 27mm-100mm。
7. preparation method according to claim 1, it is characterised in that described step 3) in the voltage of electrochemical corrosion be 1-10v。
8. preparation method according to claim 1, it is characterised in that described step 3) in time of electrochemical corrosion be 15min-180min。
9. preparation method according to claim 1, it is characterised in that described step 3) in electrolyte solution be dilute sulfuric acid, NaOH or CH3COOH。
10. the porous graphene that the preparation method as described in claim 1-9 is prepared is as the application on Substrates。
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Cited By (2)
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| CN106517333A (en) * | 2016-11-01 | 2017-03-22 | 中南大学 | Flexible conductive MoS2 thermal insulation thin film and preparation method thereof |
| CN106517993A (en) * | 2016-10-18 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Graphene/montmorillonite compound porous thin film and preparation method thereof |
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| CN106517333A (en) * | 2016-11-01 | 2017-03-22 | 中南大学 | Flexible conductive MoS2 thermal insulation thin film and preparation method thereof |
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