CN106744826B - A method of layer graphene oxide film is lacked based on esterification preparation large area - Google Patents
A method of layer graphene oxide film is lacked based on esterification preparation large area Download PDFInfo
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- CN106744826B CN106744826B CN201611027663.8A CN201611027663A CN106744826B CN 106744826 B CN106744826 B CN 106744826B CN 201611027663 A CN201611027663 A CN 201611027663A CN 106744826 B CN106744826 B CN 106744826B
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- graphene oxide
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention proposes a kind of method for lacking layer graphene oxide film based on esterification preparation large area.The carboxyl of sheet graphene oxide and hydroxyl are connected using esterification, obtain few layer of graphene oxide film of large area, solves the single layer of preparation large area or the difficulty of few layer graphene film.It selects ferric chloride (FeCl36H2O) or phosphotungstic acid hydrate is catalyst, 60 min of esterification in 98 DEG C of water-baths obtains the graphene oxide that lower sediment thing is connection completion after being centrifuged 10 min, by drop coating in clean SiO2Substrate drying, prepares graphene oxide film.Obtain graphene oxide film with a thickness of 2 ~ 3 nm, be 2 ~ 3 layers, the lamella size connected is 11 μm of 13 μ m, and there is 3.0 μm of 2.5 μ m before relative response greatly increases, and provides foundation for preparation large-area graphene film.
Description
Technical field
The present invention relates to a kind of methods for lacking layer graphene oxide film based on esterification preparation large area, belong to film
Preparation technical field.
Background technique
Carbon atom is arranged in honeycomb hexaplanar crystal with sp2 hydridization in graphene, and it is structure that thickness, which is only single layer atom,
At the basic unit of carbon nanotube and fullerene etc..It is led in electronic device, energy storage device, composite material, biological medicine etc.
Domain has wide practical use.2004, Univ Manchester UK physicist An Deliegaimu and Constantine's promise
Graphene is isolated in fertile Xiao Luofu, success from graphite, and graphene is to find most thin material so far, and its electronics moves
Shifting rate is up to 15000 cm2/ Vs is better than silicon crystal, and thermal coefficient is up to 5300 W/mK, is higher than diamond, resistivity is only
There are 10 Ω cm, lower than silver, single layer only has 2.3 % to the absorption of light, and hardness is 100 times of steel, based on more than graphene
Excellent characteristic, graphene very likely overturn the development of entire subject.However graphene makes it due to powerful Van der Waals force
Has the characteristics that hydrophobicity and easy to reunite, to bring huge challenge to graphene film is prepared.The appearance of graphene oxide
Solve agglomeration traits in preparation process very well, graphene oxide structure is substantially similar with graphene, subject to two-dimensional layer knot
Structure, interlayer contain a large amount of carboxyl and hydroxyl acidity active group, are conducive to prepare stable graphene oxide suspension, for into
One step prepares graphene film and provides raw material.
The method for preparing graphene at present mainly has physical method and chemical method, wherein mostly uses CVD in physical method
Graphene film is directly grown, advantage is to be easy to control film thickness and quality of forming film is preferable, the disadvantage is that being difficult to realize volume production.Chemistry side
Graphene oxide is generally prepared in method using improved Hummers, then further reduction obtains graphene, in preparation process
For middle graphene there are a large amount of defect, mobility is not high, and there are certain impurity, and is not easy preparation greatly using chemical method
Area single layer or few layer graphene film, but its major advantage is volume production easy to accomplish.The present invention is changed using chemical method
Into Hummers prepare graphene oxide, using esterification sheet graphene oxide is connected, to prepare large area
Single layer or few layer graphene film provide reference frame.
Summary of the invention
To solve difficulty existing for the single layer or few layer graphene film of preparation large area, the present invention proposes a kind of based on ester
Change the method that reaction preparation large area lacks layer graphene oxide film.Since graphene oxide contains a large amount of oxygen-containing functional group,
Include wherein hydroxyl and carboxyl, provides condition for esterification.The present invention will be in sheet graphene oxide using esterification
Hydroxyl and carboxyl connect.Utilize ferric chloride (FeCl36H2O) (FeCl3·6H2) or phosphotungstic acid hydrate (H O3O40PW12·
xH2O it) is used as catalyst, graphene oxide water solution is carried out as reacting precursor, 98 DEG C of water-bath, the reactant after reaction 2 hours
Centrifugation, obtaining lower sediment thing is the graphene oxide that connection is completed.Pass through drop coating to SiO2Drying prepares big face on substrate
The few layer graphene oxide film of product.The atomic force microscope images of sheet graphene oxide film and a line before Fig. 1 esterification
The height map at place, lamella size are 2.5 μm × 3.0 μm, are single thin film with a thickness of 0.83 nm.After Fig. 2 esterification
The atomic force microscope images and the height map at b line of sheet graphene oxide film, the lamella after esterification aoxidize stone
Black alkene film dimensions are 13 μm × 11 μm, are greatly increased compared to being had before esterification by the lamella size that Fig. 1 is shown.Through
Lamella graphene oxide film after esterification is layer 2-3 with a thickness of 2 ~ 3 nm, for few layer film, compared to before esterification
The lamellar spacing shown by Fig. 1 increases to few layer film by single thin film, is because graphene oxide interlayer also contains a large amount of hydroxyl
Base and carboxyl, esterification can equally make to link between sheet graphene oxide layer and layer, will increase the thickness of film, but
Thickness is can be controlled in several layers of ranges of few layer film, still significant.
Specific embodiment
The present invention relates to a kind of methods for lacking layer graphene oxide film based on esterification preparation large area, are based primarily upon
Esterification connects sheet graphene oxide, large area single layer or few layer graphene oxide film is prepared, wherein utilizing
The colloidal silica graphene of Hummers method preparation is improved as reacting precursor, ferric chloride (FeCl36H2O) (FeCl3·6H2O it) is used as and urges
Agent, specific implementation method are as follows:
1. dilution obtains colloidal silica graphene by improving Hummers method, suitable FeCl is added3·6H2O is placed in super
30 min in sound instrument.
2. the reactant after ultrasound is placed in heating water bath to 98 DEG C, 60 min are reacted.
3. the reactant after water-bath adds appropriate amount of deionized water to dilute, it is centrifuged later, takes lower sediment thing.
4. prepared by graphene oxide film: suitable dehydrated alcohol being added into sediment and is diluted, takes suitable dilute
Reactant drop coating after releasing is in clean SiO2On substrate, it is placed in 15 min in 80 DEG C of baking ovens.
Detailed description of the invention:
Height map before Fig. 1 esterification at the atomic force microscope images of sheet graphene oxide film and a line
Height map after Fig. 2 esterification at the atomic force microscope images of sheet graphene oxide film and b line.
Claims (1)
1. a kind of method for lacking layer graphene oxide film based on esterification preparation large area, specific steps include in following
Hold:
A. colloidal silica graphene is prepared using improvement Hummers method, configures a certain proportion of colloidal silica graphene and catalysis
The aqueous solution of agent is ultrasonically treated 30min；
B. the aqueous solution of graphene oxide and catalyst is placed in water-bath and is heated to 98 DEG C, 60min；
C. add deionized water to dilute to the reactant after water-bath, be centrifuged 10min at 8000rpm, take lower sediment thing；
D. suitable dehydrated alcohol is added into sediment to be diluted, the reactant drop coating after taking appropriate dilution is in cleaning
SiO2On substrate, it is placed in 15min in 80 DEG C of baking ovens, prepares graphene oxide film；
Wherein, catalyst selects ferric chloride (FeCl36H2O) or phosphotungstic acid hydrate.
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| CN201611027663.8A CN106744826B (en) | 2016-11-22 | 2016-11-22 | A method of layer graphene oxide film is lacked based on esterification preparation large area |
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| CN201611027663.8A CN106744826B (en) | 2016-11-22 | 2016-11-22 | A method of layer graphene oxide film is lacked based on esterification preparation large area |
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| CN106744826A CN106744826A (en) | 2017-05-31 |
| CN106744826B true CN106744826B (en) | 2018-12-14 |
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| KR101681950B1 (en) * | 2009-01-15 | 2016-12-05 | 삼성전자주식회사 | Method for modifying graphene edge and graphene obtained thereby |
| EP2432733A4 (en) * | 2009-05-22 | 2016-01-20 | Univ Rice William M | Highly oxidized graphene oxide and methods for production thereof |
| KR101315285B1 (en) * | 2011-09-16 | 2013-10-07 | 한국기계연구원 | A large-area Graphene sheet and method for manufacturing thereof |
| GB201204170D0 (en) * | 2012-03-09 | 2012-04-25 | Bio Nano Consulting | Cross-linked graphene networks |
| CN103450641B (en) * | 2012-05-30 | 2016-01-20 | 中国科学院理化技术研究所 | A kind of Polybutylene succinate/graphene oxide composite material and preparation method thereof |
| CN104241650B (en) * | 2013-06-14 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Composite positive pole based on three-dimensional grapheme and preparation method thereof |
| US10214422B2 (en) * | 2013-10-16 | 2019-02-26 | Research & Business Foundation Sungkyunkwan University | Interlayer distance controlled graphene, supercapacitor and method of producing the same |
| CN104945636B (en) * | 2015-05-13 | 2017-06-13 | 华南师范大学 | A kind of composite, Its Preparation Method And Use |
| CN105504700B (en) * | 2015-10-27 | 2017-12-19 | 济南圣泉集团股份有限公司 | A kind of composite polyester material containing graphene, preparation method and purposes |
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