CN108862247B - Gas molecule detection composite membrane - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000001514 detection method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 85
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 abstract description 34
- 239000002120 nanofilm Substances 0.000 abstract description 19
- 210000002469 basement membrane Anatomy 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000002346 layers by function Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a gas molecule detection membrane, which is obtained by the following method: depositing a functional layer with a nano-scale thickness on the surface of the graphene oxide film deposited on the AAO substrate, and then stripping the graphene-based composite nano film by using a water stripping method. The invention avoids two stripping means of reduction stripping and etching stripping, ensures that the stripped graphene film is not damaged at all, and keeps the original form, structure and performance of the graphene film on the AAO base film. Meanwhile, the AAO basement membrane is not damaged at all and can be recycled. Due to the small thickness of the graphene film, even reaching several nanometers, the detection film has extremely high sensitivity.
Description
Technical Field
The invention relates to the field of sensors, in particular to a gas molecule detection composite membrane.
Background
Since 2010, graphene and derivatives thereof have gained attention in various fields due to their excellent physicochemical properties. Graphene oxide is the most important precursor for preparing graphene, and simultaneously has unique physical properties, a large number of defects, oxygen-containing functional groups and the like, so that the graphene oxide has high optical transparency, high hydrophilicity, high band gap and the like. Based on this, it has gained a great deal of attention in the detection of humidity.
At present, the graphene oxide is mainly prepared by methods such as dripping, spin coating and spraying in the aspect of humidity detection, and the method has the following defects: firstly, the surface structure is not controllable; secondly, uniformity is not controllable; thirdly, the thickness is not controllable; fourth, the internal structure of the membrane is not controllable. By combining the factors, the graphene oxide-based humidity detection film does not have good linear response and has long response time.
To this end, we designed a nano-thick folded graphene film. The response area of gas molecule detection is guaranteed by the corrugated structure. Due to the nanoscale thickness and the numerous hollow structures on the surface of the chemical graphene oxide, gas can quickly penetrate through the whole membrane, and the high responsiveness and short response time of the membrane are ensured.
In addition, the graphene is not a universal material, and under the special application condition, the polymer or the metal can make up the deficiency of the graphene, so that the film meets the application requirement. Based on the method, a separation method of the nano thick graphene composite film is designed, firstly, graphene is filtered to form a film, and then metal or inorganic nanoparticles and the like are uniformly attached to the surface of the graphene in a filtering, spin coating, magnetron sputtering and other modes to prepare the graphene/inorganic nanoparticle (or metal) composite film. And then preparing the graphene composite membrane floating on the water surface by using a method for separating the graphene from the substrate water.
Disclosure of Invention
The invention aims to provide a gas molecule detection composite membrane aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a gas molecule detection composite membrane is prepared by the following method:
(1) carrying out suction filtration on the AAO base membrane to obtain a graphene oxide membrane;
(2) compounding a metal oxide layer or a metal layer on the surface of the graphene oxide base membrane to form an ultrathin film;
(3) placing the AAO carrying the membrane structure on the water surface with the surface on which the ultrathin membrane is positioned facing upwards; pressing the AAO to enable the AAO to sink, and obtaining the graphene-based ultrathin film floating on the water surface.
(4) Fishing up the graphene-based ultrathin film floating on the water surface from bottom to top by using a silicon wafer substrate, so that the graphene film is laid on the surface of the substrate;
(5) evaporating water in the graphene-based ultrathin film at room temperature to enable the water content to be more than 50 wt%; and (4) freeze-drying the evaporated graphene-based ultrathin film, and separating the graphene oxide film from the surface of the silicon wafer.
(6) And reducing the graphene-based ultrathin film to ensure that the conductivity of the graphene-based ultrathin film is more than 50S/cm.
Further, the thickness of the ultrathin film is less than 100 nm.
Further, the thickness of the graphene-based base film is less than 100 nm.
Further, in step 3, the pressing position is an edge of the AAO.
Further, the thickness of the graphene-based base film is 4 nm.
Further, the porosity of the surface of the AAO base film is not less than 40%.
Further, the metal layer is Pt, and the composite method is magnetron sputtering.
Further, the metal oxide layer is SnO2、ZnO、WO3、Cu2O、Co3O4、NiO、In2O3、MoO2. The composite method comprises magnetron sputtering and spin coating.
Further, in the step 5, the reduction method comprises chemical reduction and thermal reduction; the reducing agent adopted by the chemical reduction is selected from hydrazine hydrate and hydroiodic acid; the thermal reduction is specifically as follows: reducing by water vapor at 200 ℃.
The invention has the beneficial effects that: the film is prepared by a suction filtration method, so that the uniformity of the composite film and the stability of a device are ensured; the thickness of the graphene composite membrane is controlled at a nanometer level by adopting a water transfer method, the responsivity of the membrane is improved, and meanwhile, microscopic folds are introduced in the transfer process, so that the response speed of the membrane is increased. The whole process is simple, green and easy to operate.
Drawings
Fig. 1 is a schematic flow chart of peeling a graphene film from an AAO base film.
Fig. 2 is a graph showing an experimental process of peeling a graphene film from an AAO base film of example 1.
Fig. 3 is an atomic force microscope image of the graphene film obtained in example 1.
Fig. 4 is a scanned view of the graphene-based Pt nanomembrane prepared in example 2.
Fig. 5 is an atomic force microscope image of the graphene-based Pt nanomembrane prepared in example 2.
FIG. 6 is a graphene-based SnO prepared in example 32Atoms of the nano-filmForce microscopy pictures.
Fig. 7 is an atomic force microscope image of the graphene film prepared in example 4.
FIG. 8 shows graphene-based MoO prepared in example 52Atomic force microscopy of the nanomembrane.
Fig. 9 is a graph showing an experimental process of peeling a graphene film from an MCE base film of comparative example 1.
Detailed Description
Example 1
By controlling the concentration of the graphene solution, carrying out suction filtration on an AAO (anodic aluminum oxide) base film by a suction filtration method to obtain an ultrathin reduced graphene oxide film; placing an AAO base film (with a porosity of 40%) with a reduced graphene oxide film attached to the surface on a water surface with the graphene film facing upward, as shown in fig. 1a and 2 a; pressing the AAO base membrane as in fig. 2b, the AAO base membrane starts to sink as in fig. 2c, and finally, the AAO base membrane sinks to the bottom of the cup, and the graphene membrane (inside the dashed circle) floats on the water surface as in fig. 1b and 2 d.
And (3) fishing up the graphene film floating on the water surface from bottom to top by using a silicon wafer substrate, paving the graphene film on the surface of the substrate, naturally airing, and testing the thickness of the graphene film to be 4nm by using an atomic force microscope, wherein the thickness is shown in figure 3.
Example 2
(1) According to the suction filtration method in the embodiment 1, the reduced graphene oxide base membrane with the thickness of 4nm is obtained by suction filtration on the AAO base membrane.
(2) Sputtering a Pt nano layer on the surface of the graphene film in the step 1 by a magnetron sputtering method;
(3) the surface of the ultrathin film is upward and is placed on the water surface; pressing the AAO edge, the AAO basement membrane begins to sink, and finally, the AAO basement membrane sinks to the bottom of the cup, the graphite membrane floats on the water surface, and the graphene-based Pt nano-membrane is successfully stripped.
Fishing up the graphene-based Pt nano film floating on the water surface from bottom to top by using a silicon wafer substrate, paving the graphene-based Pt nano film on the surface of the substrate, evaporating the water in the film for 30min at room temperature, and measuring the water content to be 67 wt%; freeze-drying the evaporated graphene-based Pt nano-film, and separating the film from the surface of a silicon wafer, wherein the surface of the film has a large number of folds, as shown in FIG. 4; the thickness was 18nm as measured by atomic force microscopy, as shown in FIG. 5.
Transferring the mixture to water vapor at 200 ℃ for reduction for 1h, and measuring the conductivity of the mixture after drying to be 54S/cm. And spraying gold electrodes at two ends of the graphene film for outputting electric signals.
Placing the reduced graphene composite membrane (with the size of 2mm) in H2The resistance change was monitored in real time in a 1ppm vacuum glove box as shown in Table 1.
Example 3
(1) According to the suction filtration method in the embodiment 1, the reduced graphene oxide base membrane with the thickness of 4nm is obtained by suction filtration on the AAO base membrane.
(2) Performing suction filtration SnO on the surface of the graphene film in the step 1 by a magnetron sputtering method2A nanolayer;
(3) the surface of the ultrathin film is upward and is placed on the water surface; pressing the AAO edge, the AAO basement membrane begins to sink, and finally, the AAO basement membrane sinks to the bottom of the cup, the graphite film floats on the water surface, and the graphene-based SnO2 nano-film is successfully stripped.
Graphene-based SnO floating on water surface by using silicon wafer substrate2The nano film is fished up from bottom to top, so that the graphene-based SnO2Spreading the nano film on the surface of the substrate, evaporating the water in the film for 30min at room temperature, and measuring the water content to be 54 wt%; carrying out evaporation treatment on the graphene-based SnO2Freeze-drying the nano film, and separating the nano film from the surface of the silicon wafer, wherein the surface of the nano film has a large number of folds; the thickness was 38nm as measured by atomic force microscopy, as shown in FIG. 6.
Transferring to hydriodic acid steam for reduction for 0.5h, and drying to obtain the conductivity of 86S/cm. And spraying gold electrodes at two ends of the graphene film for outputting electric signals.
The reduced graphene composite membrane (size 2mm) was placed in a vacuum glove box with NO of 10ppm, and the change in resistance was monitored in real time as shown in table 1.
Example 4
The method comprises the steps of (1) obtaining an ultrathin graphene oxide film by suction filtration on an AAO (alkaline-earth oxide) base film through a suction filtration method by controlling the concentration of a graphene solution; placing the AAO base film (with the porosity of 60%) with the graphene oxide film attached to the surface on the water surface with the surface of the graphene film facing upwards, pressing the edge of the AAO base film to enable the AAO base film to start sinking, finally enabling the AAO base film to sink to the cup bottom, enabling the graphene film to float on the water surface, and successfully stripping the graphene film.
And (3) fishing up the graphene film floating on the water surface from bottom to top by using a silicon wafer substrate, paving the graphene film on the surface of the substrate, naturally airing, and testing the thickness of the graphene film to be 14nm by using an atomic force microscope, wherein the thickness is shown in figure 7.
Example 5
(1) According to the suction filtration method of the embodiment 4, the graphene oxide base membrane with the thickness of 14nm is obtained by suction filtration on the AAO base membrane.
(2) Filtering MoO on the surface of the graphene film in the step 1 by a filtering method2A nanolayer;
(3) the surface of the ultrathin film is upward and is placed on the water surface; pressing the AAO edge, the AAO basement membrane begins to sink, and finally, the AAO basement membrane sinks to the bottom of the cup, the graphite membrane floats on the water surface, and graphene-based MoO2The nanofilm was successfully peeled off.
Fishing up the graphene-based MoO2 nano film floating on the water surface from bottom to top by using a silicon wafer substrate, paving the graphene-based polyvinyl alcohol nano film on the surface of the substrate, evaporating the water in the film for 30min at room temperature, and measuring the water content to be 89 wt%; evaporating the graphene-based MoO2Freeze-drying the nano film, and separating the nano film from the surface of the silicon wafer, wherein the surface of the nano film has a large number of folds; the thickness was 66nm as measured by atomic force microscopy, as shown in FIG. 8.
Transferring to hydriodic acid steam for reduction for 0.5h, and measuring the conductivity of the product after drying to be 84S/cm. And spraying gold electrodes at two ends of the graphene film for outputting electric signals.
Placing the reduced graphene composite membrane (with the size of 2mm) in H2The resistance change was monitored in real time in a vacuum glove box with S of 10ppm, as shown in Table 1.
The remaining composite films and their response properties are shown in table 1.
TABLE 1
Comparative example 1
(1) The graphene oxide-based membrane with a thickness of 14nm was obtained by suction filtration using an MCE substrate membrane (porosity 60%) according to the suction filtration parameters as in example 4.
(2) Filtering the polyvinyl alcohol layer on the surface of the graphene film in the step 1 by a filtering method;
(3) the surface of the ultrathin film is placed on the water surface, the edge of the MCE substrate film is pressed as shown in fig. 9a, the MCE substrate film does not sink, and as shown in fig. 9b, the graphene-based polyvinyl alcohol nano film fails to be stripped, so that a single graphene-based polyvinyl alcohol nano film cannot be obtained.
The filtration method is the most uniform method for preparing graphene films, and can control the thickness of a graphene film by regulating and controlling the concentration under a certain amount of filtration liquid, the thickness can be the lowest graphene, the newly added graphene gradually fills the gap of the first graphene layer under the action of pressure along with the increase of the concentration of the graphene, so that the first graphene layer is gradually and completely filled, and then the first graphene layer is developed into a second graphene layer, and the steps are continuously repeated, so that the graphene nano film with the thickness of 2 to ten thousand graphene layers can be prepared. Therefore, a graphene film with a thickness of 4nm can be obtained by a person skilled in the art through simple experimental parameter adjustment, and similarly, methods for preparing thin films by spin coating, magnetron sputtering and the like are mature technical means in the industry.
Claims (9)
1. The preparation method of the gas molecule detection composite membrane is characterized in that the gas molecule detection composite membrane is formed by compounding a wrinkled metal oxide layer or a metal layer and a reduced graphene oxide ultrathin membrane, and is prepared by the following steps:
(1) carrying out suction filtration on the AAO base membrane to obtain a graphene oxide membrane;
(2) compounding a metal oxide layer or a metal layer on the surface of the graphene oxide base membrane to form an ultrathin film;
(3) placing the AAO carrying the membrane structure on the water surface with the surface on which the ultrathin membrane is positioned facing upwards; pressing the AAO to enable the AAO to sink, so that the graphene-based ultrathin film floating on the water surface is obtained;
(4) fishing up the graphene-based ultrathin film floating on the water surface from bottom to top by using a silicon wafer substrate, so that the graphene film is laid on the surface of the substrate;
(5) evaporating water in the graphene-based ultrathin film at room temperature to enable the water content to be more than 50 wt%; freeze-drying the evaporated graphene-based ultrathin film, and separating the graphene oxide film from the surface of the silicon wafer;
(6) and reducing the graphene-based ultrathin film to ensure that the conductivity of the graphene-based ultrathin film is more than 50S/cm.
2. The method of claim 1, wherein the ultra-thin film has a thickness of less than 100 nm.
3. The method according to claim 1, wherein the graphene-based film has a thickness of less than 100 nm.
4. The production method according to claim 1, wherein in the step (3), the pressing position is an edge of the AAO.
5. The method according to claim 1, wherein the graphene-based base film has a thickness of 4 nm.
6. The production method according to claim 1, wherein the porosity of the surface of the AAO base film is not less than 40%.
7. The method according to claim 1, wherein the metal layer is Pt and the composite method is magnetron sputtering.
8. The method according to claim 1, wherein the metal oxide layer is SnO2、ZnO、WO3、Cu2O、Co3O4、NiO、In2O3Or MoO2The composite method is magnetron sputtering or spin coating.
9. The method according to claim 1, wherein in the step (5), the reduction method comprises chemical reduction, thermal reduction; the reducing agent adopted by the chemical reduction is selected from hydrazine hydrate and hydroiodic acid; the thermal reduction is specifically as follows: reducing by water vapor at 200 ℃.
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| CN102275902B (en) * | 2010-06-12 | 2013-04-17 | 中国科学院金属研究所 | Method for preparing graphene material by reducing graphene oxide |
| CN102897750B (en) * | 2011-07-29 | 2014-09-10 | 浙江大学 | PrPrearation method for graphene film |
| CN104039695B (en) * | 2011-09-19 | 2018-06-05 | 卧龙岗大学 | Redox graphene and its production method |
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| EP2801551A1 (en) * | 2013-05-08 | 2014-11-12 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Graphene with very high charge carrier mobility and preparation thereof |
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| CN103833030B (en) * | 2014-01-16 | 2016-01-06 | 中国科学院青岛生物能源与过程研究所 | A kind of method of big area transfer CVD graphene film |
| WO2015149116A1 (en) * | 2014-04-04 | 2015-10-08 | Commonwealth Scientific And Industrial Research Organisation | Graphene process and product |
| CN104211055B (en) * | 2014-09-10 | 2015-11-18 | 浙江碳谷上希材料科技有限公司 | A kind of preparation method of Graphene metallic nanoparticle composite membrane |
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