CN104649257A - Multi-aperture graphene film manufacturing method and gas separation element - Google Patents
Multi-aperture graphene film manufacturing method and gas separation element Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000926 separation method Methods 0.000 title claims abstract description 14
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- 230000008569 process Effects 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000012795 verification Methods 0.000 abstract description 2
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 18
- 239000004926 polymethyl methacrylate Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000007547 defect Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
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- 238000004528 spin coating Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
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- 238000009826 distribution Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000002161 passivation Methods 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020852 Hypertonia Diseases 0.000 description 1
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- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
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Abstract
The invention discloses a multi-aperture graphene film manufacturing method. In the method, an energy beam is used for radiating the graphene film with lattice imperfection, as a result, the carbon bonding with lattice imperfection in graphene carbon ring hexagonal structure is broken, aperture is generated, and the multi-aperture graphene film is generated; moreover, size of the aperture is controlled by regulation on concentration of the lattice imperfection and/or radiation intensity of the energy beam. The invention further discloses a gas separation element using the multi-aperture graphene film manufactured by the method. By the method, the graphene film with gas permeation aperture is prepared actually for the first time, and application of the graphene film in the aspect of gas separation is realized successfully; in the method, size of aperture can be controlled as needed, moreover, the preparation technology is simple, the implementation cost is low, so that the method is suitable for large-scale industrial application; the gas separation element provided by the invention has very strong selectivity and high permeability to gas molecules, and by experimental verification, separation coefficient of the gas separation element to H2/N2 at normal temperature is up to 260.
Description
Technical field
The present invention relates to the manufacture method of Graphene (Graphene) film, particularly relate to a kind of manufacture method that can be used for the multiple aperture graphene film of gas delivery.
Background technology
With the inorganic material film that metal, metal oxide, pottery, carbon, sintered glass are representative, due to the physics of excellence, chemistry and biological nature, be widely used in gas delivery, sea water desaltination, food-processing, wastewater treatment and medicine and other fields.But mineral membrane has the highly selective of gas and rate of permeation treats the difficult problem that need solve simultaneously.Simultaneously under maintenance hypertonicity and highly selective situation, the resistance to gentle chemical resistance how improving film is another challenge that mineral membrane is separated application.Solving these difficult problems Main way is the novel inorganic mould material seeking to have the distribution of controlled uniform pore size, ultra-thin, high mechanical strength and improved corrosion.
Compared with traditional material, desirable Graphene has the thickness of monoatomic layer, uniform pore size distribution, peculiar and outstanding mechanics, calorifics and electric property.Theoretically, the thickness of the monoatomic layer of Graphene and uniform pore size distribution should be desirable infiltration and separatory membrane.But individual layer intrinsic Graphene is extensively thought to gas it is completely impervious.One of its reason is the aperture size (aperture ~ 0.2nm) of Graphene, is enough to impermeable all gas and liquid phase molecule.Even if multiple-layer stacked graphene film, due to the stack mode of their densification and the infiltration lane of shortage gas, be considered to equally to be used for membrane sepn application.Manually modified like this Graphene aperture is the direction of graphene film gas-permeable application.There is researchist to imagine the electrical charge rejection being reduced its surface by the passivation of selection molecule, gas can be passed through.But because its complicated operation, condition are wayward, molecule PASSIVATION MECHANISM such as to be still not clear at the impact of factor, also mainly rests on the stage of molecular dynamics simulation at present.
In summary, although technology multiple aperture Graphene being used for gas-permeable has good prospect, there is no the multiple aperture graphene preparation method being applicable to practical application at present and be suggested.
Summary of the invention
Technical problem to be solved by this invention is to overcome prior art deficiency, a kind of manufacture method of multiple aperture graphene film is provided, utilize the multiple aperture graphene film manufactured by the method to have extremely strong selectivity and high permeability to gas molecule, pore size can adjust as required simultaneously.
The present invention specifically solves the problems of the technologies described above by the following technical solutions:
A manufacture method for multiple aperture graphene film, utilizes energy-beam to carry out radiation to the graphene film with lattice imperfection, and the bond with carbon in Graphene carbocyclic ring hexagonal structure with lattice imperfection is interrupted, and produces aperture, thus generates multiple aperture graphene film; And controlled by the adjustment concentration of lattice imperfection and/or the size of the yield of radiation of energy-beam to described aperture.
Described energy-beam can be electron beam, photon beam, ionic fluid etc., in order to make lattice imperfection effectively change into can supplied gas infiltration aperture, broken ring can not be produced to normal crystalline network again simultaneously, preferably, the plasma beam that the electron beam that the ionic fluid of described energy-beam to be energy region be 5MV ~ 10MV, energy region are 1 KeV ~ 100KeV, energy region are 0.1 W ~ 500W, or energy region is the photon beam of 0.1 mJ ~ 500mJ.
Utilize the multiple aperture graphene film of aforesaid method manufacture can obtain following gas delivery element:
A kind of gas delivery element, comprises perforated substrate and is attached to the gas separation membrane of at least one side surface of perforated substrate, and described gas separation membrane is for utilizing the multiple aperture graphene film that described in above arbitrary technical scheme, method manufactures.
Compared to existing technology, the present invention has following beneficial effect:
The present invention is actual has first prepared the graphene film with gas-permeable aperture, successfully achieves the application of graphene film in gas delivery; The present invention produces lattice imperfection consciously in intrinsic graphene film, and utilize the energy-beam radiation of certain energy region to make lattice imperfection change gas-permeable aperture into, can control pore size as required, and preparation technology is simple, realize with low cost, be suitable for large-scale industrial application; Gas delivery element of the present invention has extremely strong selectivity and high permeability to gas molecule, through experimental verification, at normal temperatures to H
2/ N
2separation factor up to 260.
Accompanying drawing explanation
Fig. 1 is that complete Graphene contrasts schematic diagram with the crystalline network of the defective Graphene of band;
Fig. 2 is the graphene film structural representation that in embodiment, chemical Vapor deposition process prepares;
Fig. 3 is the graphene film structural representation of spin coating PMMA in embodiment;
Fig. 4 is the process schematic removing Cu tinsel in embodiment;
Fig. 5 is by process schematic that the graphene film of spin coating PMMA is combined with target substrate in embodiment;
Fig. 6 is the process schematic of the PMMA removing graphene membrane surface in embodiment.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in detail:
As described by background technology part, although single or multiple lift intrinsic Graphene is considered to desirable infiltration and separatory membrane in theory, but due to lack can supplied gas infiltration passage, in fact cannot be applied to membrane sepn, also not have the technology that can produce gas-permeable aperture in graphene film to be disclosed at present.In order to address this problem, thinking of the present invention in graphene film, produces lattice imperfection consciously, then the energy-beam radiation of certain energy region is utilized, when not destroying normal graphene-structured, the bond with carbon in Graphene carbocyclic ring hexagonal structure with lattice imperfection is interrupted, thus the aperture that supplied gas passes through can be produced, and then obtain the multiple aperture graphene film that can be used for membrane sepn; Also can according to actual needs, be controlled by the adjustment concentration of lattice imperfection and/or the size of the yield of radiation of energy-beam to described aperture simultaneously.
The technology of preparing of existing Graphene roughly comprises this several more ripe method following: micromechanics stripping method, chemical Vapor deposition process (Chemical Vapor Deposition, CVD), oxidation-reduction method, solvent stripping method, solvent-thermal method, and the preparation method that high temperature reduction method, photoreduction method, epitaxial crystal growth method, microwave method, arc process etc. are newer.But, no matter take which kind of method, be limited to processing condition, the actual grapheme material prepared existing defects more or less, namely Fig. 1 shows complete Graphene and contrasts with the crystalline network of the defective Graphene of band, wherein left side is complete Graphene (or being called perfect Graphene) structure, and right side is the defective graphene-structured of band.Because defect can have an impact to the electrical specification of Graphene and physical property, therefore how investigator generally eliminates in research or reduces the defect of Graphene, to obtain perfect grapheme material as far as possible.In fact, these existing in Graphene defects are utilizable.Found through experiments, under the effect of photon, plasma body, electronics homenergic bundle, the bond with carbon in Graphene carbocyclic ring hexagonal structure with lattice imperfection can preferentially be interrupted, and normal bond with carbon is then unaffected; When energy intensity is in certain limit, the aperture formed is enough to the needs meeting gas-permeable, therefore can utilize the next multiple aperture graphene film for the preparation of gaseous jet simulation of this discovery.
For the ease of public understanding, the manufacturing processed of gas delivery element of the present invention is described with a specific embodiment below, specifically comprises the following steps:
Steps A, in target substrate preparation there is the graphene film of lattice imperfection.
As previously stated, be limited to processing condition, the actual grapheme material prepared of existing various method existing defects more or less, such as, in the CVD graphene growth process of reality, due to the existence of impure gas and impurity, in the Graphene of growth, inevitably introduce impurity, thus produce lattice imperfection in various degree.Therefore, directly can adopt existing various graphene film technology of preparing in target substrate, prepare the graphene film with lattice imperfection, or obtain required defect further by adjusting process parameter or active doping.First adopt chemical Vapor deposition process to prepare graphene film on the metallic substrate in the present embodiment, then metal base displaced by target substrate, its process is specific as follows:
Steps A 1, use chemical Vapor deposition process prepare single layer graphene film in Cu metal base, specifically comprise the following steps:
1, pre-treatment silica tube: vacuumize in silica tube with vacuum pump, when the air pressure in each silica tube reduces, is filled with argon gas, makes air pressure increase, repeatable operation 3-5 time, to ensure in silica tube as pure argon gas.
2, heat up: in silica tube, put into Cu paper tinsel, pass into H simultaneously
2and Ar, the temperature in silica tube is warmed up to 1000 DEG C with constant rate of speed.
3, anneal: keep H
2constant with the intake of Ar, Cu paper tinsel is annealed 20-30min at the temperature of 1000 DEG C.
4, growing graphene: open methane gas cylinder, passes into appropriate methane, H
2and Ar, growth time is 3-10min, obtains sample as shown in Figure 2.
5, cool: close methane gas cylinder, continue the flow keeping hydrogen and argon gas, make sample cool to room temperature.
Steps A 2, graphene film to be transferred in required target substrate, specifically comprises the following steps:
The PMMA(polymethylmethacrylate of 1, configuration appropriateness) solution, solute is PMMA, and solvent is chlorobenzene.
2, as shown in Figure 3, spin coating one deck PMMA film in the copper metal foil surface having graphene film is being grown, first stage: 500r/5s, subordinate phase: 2000r/20s.
3, the Cu tinsel of PMMA film spin coating is had to dry, so that PMMA film hardening at drying glue platform.
4, Cu metal level with fine sandpaper, Graphene unnecessary for the Cu metal back side, PMMA film wiped out, so that can contact with etching solution completely.
5, configuration concentration is the FeCl of 0.5mol/L
3solution or concentration are the Fe (NO of 0.5mol/L
3)
3solution, and in culture dish, pour this solution into.
6, have the Cu tinsel of PMMA to put in this solution spin coating, after 3 hours, metallic copper is complete by solution etches, and only remaining PMMA/Graphene composite membrane swims in above solution, and its process as shown in Figure 4.
7, use deionized water FeCl
3solution replacement falls, and repeatedly replaces 5 times, and ensure deionized water only remaining pure in culture dish, its process as shown in Figure 5.
8, target substrate is put in deionized water, it is made to depart from aqueous environment after PMMA/ Graphene and target substrate are attached together, the composite membrane that PMMA/ Graphene/target substrate is formed is put on drying glue platform and dries, graphene film and target substrate are close to.
9, PMMA/ Graphene/target substrate composite membrane is placed in empty culture dish, dripping some PMMA solution again at sample surfaces makes the PMMA film of solidification soften, acetone soln is added afterwards again to dissolve PMMA film in culture dish, as shown in Figure 6, such Graphene has been deposited in target substrate its process.
The graphene film with lattice imperfection can be obtained in target substrate by above step, can lead in the process
Overregulate corresponding processing condition to control defect type and defect density.Such as, by control H
2dividing potential drop, the vacuum tightness of background or the time of reaction obtain the Graphene of the different number of plies, different defect density; Or adjust defect type and concentration further by initiatively adulterating.
Step B, utilize energy-beam to carry out radiation to the described graphene film with lattice imperfection, make the lattice imperfection of graphene film change aperture into, thus generate multiple aperture graphene film.
Described energy-beam can be described energy-beam can be electron beam, photon beam, ionic fluid etc., in order to make lattice imperfection effectively change into can supplied gas infiltration aperture, broken ring can not be produced to normal crystalline network again simultaneously, preferably, the plasma beam that the electron beam that the ionic fluid of described energy-beam to be energy region be 5MV ~ 10MV, energy region are 1 KeV ~ 100KeV, energy region are 0.1 W ~ 500W, or energy region is the photon beam of 0.1 mJ ~ 500mJ.The optimum configurations of concrete energy-beam can be determined by test in advance, such as, the energy-beam of a series of different parameters can be utilized to carry out radiation to identical sample, then analysis to measure is carried out to the aperture of the graphene film after the energy-beam process of variant parameter, the corresponding relation (relation curve, relation list or relational expression) between different-energy bundle parameter and aperture can be obtained according to the analysis to measure result in aperture.According to actual needs, by the parameter such as intensity, radiated time of the energy-beam parameter obtained the in advance energy-beam corresponding to the correspondence setting between aperture.Inside diameter measurement in graphene film can use the means such as atomic force microscope (Atomic force microscopy), scanning tunneling microscope (Scanning tunneling microscopy), scanning electron microscope (Scanning electron microscopy) and transmission electron microscope (Transmitting Electron Microscopy).COHERENT type laser apparatus (KrF is utilized in the present embodiment, λ=248nm) Graphene is carried out to the radiotreatment of a series of different condition, laser energy is adjusted to respectively: 1mJ, 5 mJ, 10 mJ, 20 mJ, 30 mJ, 40 mJ, 50 mJ, 100 mJ, frequency is 1Hz, and umber of pulse is respectively 2,5,10.
In order to verify effect of the present invention, utilize the separation performance of chromatogram to the preparation-obtained gas delivery element of above embodiment to test, test condition is under room temperature normal pressure and the H of appropriateness
2, N
2, He, CH4, CO, CO2, Measuring Time is 20min/ time, according to going out peak position and peak area is converted into H
2, N
2penetrating quality, calculate separation factor.Test result shows, and the gas delivery element utilizing the inventive method to prepare is at normal temperatures to H
2/ N
2separation factor up to 260, multiple aperture graphene film prepared by sufficient proof the inventive method has excellent gas separating property.The inventive method can control pore size as required, and preparation technology is simple, realizes with low cost, is suitable for large-scale industrial application.
Claims (7)
1. the manufacture method of multiple aperture graphene film, it is characterized in that, utilize energy-beam to carry out radiation to the graphene film with lattice imperfection, the bond with carbon in Graphene carbocyclic ring hexagonal structure with lattice imperfection is interrupted, produce aperture, thus generate multiple aperture graphene film; And controlled by the adjustment concentration of lattice imperfection and/or the size of the yield of radiation of energy-beam to described aperture.
2. the manufacture method of multiple aperture graphene film as claimed in claim 1, is characterized in that, the ionic fluid of described energy-beam to be energy region be 5MV ~ 10MV.
3. the manufacture method of multiple aperture graphene film as claimed in claim 1, is characterized in that, the electron beam of described energy-beam to be energy region be 1 KeV ~ 100KeV.
4. the manufacture method of multiple aperture graphene film as claimed in claim 1, is characterized in that, the plasma beam of described energy-beam to be energy region be 0.1 W ~ 500W.
5. the manufacture method of multiple aperture graphene film as claimed in claim 1, is characterized in that, the photon beam of described energy-beam to be energy region be 0.1 mJ ~ 500mJ.
6. the manufacture method of multiple aperture graphene film as described in any one of Claims 1 to 5, is characterized in that, described in there is lattice imperfection graphene film be the single or multiple lift graphene film using chemical Vapor deposition process to prepare.
7. a gas delivery element, comprises perforated substrate and is attached to the gas separation membrane of at least one side surface of perforated substrate, it is characterized in that, the multiple aperture graphene film that described gas separation membrane manufactures for utilizing method described in any one of claim 1 ~ 6.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299423A (en) * | 2016-10-18 | 2017-01-04 | 无锡同春新能源科技有限公司 | Leach hydrogen with graphene film and manufacture the enhancing device of hydrogen fuel cell |
| CN109467073A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of preparation method and applications of porous carbon |
| CN110869109A (en) * | 2017-07-14 | 2020-03-06 | 国立大学法人信州大学 | Nano-window structure of graphene and method for manufacturing high-purity gas |
| CN112892240A (en) * | 2021-01-15 | 2021-06-04 | 湖南二零八先进科技有限公司 | Metal-supported graphene separation membrane and preparation method thereof |
| CN113184833A (en) * | 2021-03-23 | 2021-07-30 | 北京大学 | Preparation method of graphene membrane used as proton exchange membrane |
| CN113484399A (en) * | 2021-05-20 | 2021-10-08 | 南京工业大学 | Graphene film-based gas production testing method for metal ion battery, film assembly and preparation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299423A (en) * | 2016-10-18 | 2017-01-04 | 无锡同春新能源科技有限公司 | Leach hydrogen with graphene film and manufacture the enhancing device of hydrogen fuel cell |
| CN110869109A (en) * | 2017-07-14 | 2020-03-06 | 国立大学法人信州大学 | Nano-window structure of graphene and method for manufacturing high-purity gas |
| US11278849B2 (en) | 2017-07-14 | 2022-03-22 | Shinshu University | Graphene nanowindow structure and method for producing highly pure gas |
| CN109467073A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of preparation method and applications of porous carbon |
| CN109467073B (en) * | 2018-09-25 | 2022-04-29 | 江苏天雨环保集团有限公司 | Preparation method and application of porous carbon |
| CN112892240A (en) * | 2021-01-15 | 2021-06-04 | 湖南二零八先进科技有限公司 | Metal-supported graphene separation membrane and preparation method thereof |
| CN113184833A (en) * | 2021-03-23 | 2021-07-30 | 北京大学 | Preparation method of graphene membrane used as proton exchange membrane |
| CN113484399A (en) * | 2021-05-20 | 2021-10-08 | 南京工业大学 | Graphene film-based gas production testing method for metal ion battery, film assembly and preparation method |
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Application publication date: 20150527 |