CN104313549B - A kind of preparation method with the graphene-based film of self-cleaning function - Google Patents
A kind of preparation method with the graphene-based film of self-cleaning function Download PDFInfo
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- CN104313549B CN104313549B CN201410472524.0A CN201410472524A CN104313549B CN 104313549 B CN104313549 B CN 104313549B CN 201410472524 A CN201410472524 A CN 201410472524A CN 104313549 B CN104313549 B CN 104313549B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
Abstract
The present invention relates to a kind of preparation method with the graphene-based film of self-cleaning function, graphene oxide dispersion and titanium oxide dispersion are prepared respectively, and graphene oxide/titanium oxide dispersion will be obtained after graphene oxide dispersion and titanium oxide dispersion blending, graphene oxide/titanium oxide dispersion is ejected into target base plate, graphene oxide base film is obtained；Ultraviolet light graphene oxide base film, is reduced to it, is obtained with the graphene-based film of self-cleaning function.Compared with prior art, the present invention prepares graphene oxide base film by spraying, and ultraviolet light is being utilized, while prepared graphene-based film has certain electric conductivity, it may have certain self-cleaning function.The graphene-based film of the present invention can further be applied to the fields such as graphene-based conductive coating and graphene-based surface strain sensor simultaneously.
Description
Technical field
The present invention relates to a kind of preparation method of graphene-based film, there is self-cleaning function graphite more particularly, to one kind
The preparation method of alkenyl film, belongs to film material with function technical field.
Background technology
Graphene has good transmitance, and theoretical and experimental results show, single-layer graphene absorb 2.3% it is visible
Light, i.e. light transmittance are 97.7%.Each carbon atom in graphene is with sp2The mode (σ keys) of hybridized orbit and other 3 carbon originals
Son is connected, and extremely strong C-C keys cause graphene sheet layer to have excellent mechanical property.A remaining p electron orbit is vertical
In graphene planes, the pi bond with the carbon atom formation delocalization of surrounding causes electronics to be moved freely in crystal, imparts stone
The good electrical property of black alkene.Because interatomic active force is very strong, at normal temperatures, even if surrounding carbon atom is telescoped, stone
The interference that electronics in black alkene is subject to also very little.Electronics is not susceptible to scattering when being transmitted in graphene, mobility up to 2 ×
105cm2/(V·s).Its surface resistance is about 31 Ω/sq, and electrical conductivity is up to 106S/m, is the optimal material of electric conductivity at room temperature.
The preparation method of graphene is broadly divided into CVD, liquid phase physics stripping method, epitaxial growth method and oxidation-reduction method.
And oxidation-reduction method is mainly manifested in following method compared to the advantage of other several methods：(1) production cost is relatively low,
(2) preparation technology is relatively simple, and (3) preparation efficiency is higher.Therefore, oxidation-reduction method prepares what is studied after graphene would is that
Important directions.Being currently based on oxidation-reduction method and preparing the method for graphene-based film mainly has vacuum filtration method, spin-coating method, from group
Dress, LangmuirBlodgett (LB) method, spraying process etc..By some reduction means during film is prepared, such as it is hydrated
Hydrazine is reduced, and HI acid reduction or thermal reduction etc. are handled graphene oxide film, finally prepare graphene-based film.Make graphite
Alkene film has following one or more of features：(1) conductive, (2) are transparent, (3) sensing etc..
Find that graphene film has during graphene film is prepared, not based on oxidation-reduction method both at home and abroad at present
There is certain self-cleaning function.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is simple, efficient, can
The preparation method with the graphene-based film of self-cleaning function of engineering expanding production.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method with the graphene-based film of self-cleaning function, comprises the following steps：
(1) prepare graphene oxide dispersion in water/ethanol or ethanol solution, the concentration of graphene oxide for 0.1~
2mg/ml, is prepared for dispersiveness and the preferable graphene oxide dispersion of stability after sonic oscillation.
It is preferred that, in described graphene oxide dispersion added with enhancing conductive material, graphene oxide with
The weight ratio for strengthening conductive material is 1: 1~10: 1.Described enhancing conductive material is CNT or metal nanometer line.
(2) Nano titanium dioxide is added in ethanol solution, it is 0.1~1mg/ml's that concentration is prepared for after ultrasonic 1h
Titanium oxide dispersion.
(3) by after graphene oxide dispersion and titanium oxide dispersion blending, appropriate ultrasound, obtain graphene oxide/
In titanium oxide dispersion, described graphene oxide/titanium oxide dispersion, the weight ratio of graphene oxide and titanium dioxide
For 1: 1~20: 1, preferably 1: 1.
(4) a certain amount of graphene oxide/titania solution dispersion liquid is taken to be added in the spray gun for being associated with air pump, in mesh
Sprayed on mark substrate, uniformly prepare graphene oxide base film.
(5) prepared film is irradiated under ultraviolet light, fluorescent tube is 175W, the distance of fluorescent tube and sample is
15cm, irradiation time is 10h, and film is reduced, and is obtained with the graphene-based film of self-cleaning function.
In the present invention, the Catalysis Principles of titanium dioxide is as follows：There is the photon of hv energy sizes when one or with big
When semiconductor energy gap Eg photon injects semiconductor, an electronics is energized into conduction band (CB) by valence band (VB), thus
A high activity electronics (e is produced on conduction band-), a hole (h+) is left in valence band, redox system is formed.Dissolving
Oxygen and water and electronics and hole interaction, the final hydroxyl for producing high activity.OH-、O2 -、OOH-Free radical has Strong oxdiative
Property, can be most of absorption in TiO2The organic pollutant degradation on surface is CO2、H2O, aoxidizes inorganic pollution or be reduced to
Harmless object.Wherein titanium dioxide can be expressed as to the reduction principle of graphene oxide：
TiO2+hv→TiO2(h+e)→C2H5OH→TiO2(e)+·C2H4OH+H+ (1)
TiO2(e)+graphene oxide(GO)→TiO2+graphene reduced(GR) (2)
Compared with prior art, the present invention has advantages below：
(1) present invention is prepared for graphene oxide/titanium dioxide mixed liquor, and it is thin to prepare graphite oxide alkenyl by spraying
Film, is utilizing ultraviolet light, while prepared graphene-based film has certain electric conductivity, it may have it is certain from
Cleaning function.
(2) effect of titanium dioxide, on the one hand shows the reduction to graphene oxide, and on the other hand showing makes film
Itself there is certain self-cleaning function, and have certain effect of murdering to the germ in surrounding environment, formaldehyde etc. has one
Fixed degradation.
(3) this method is in the reduction process of film is realized, not using such as HI acid, the noxious material such as hydrazine hydrate, but
The titanium dioxide of environmental protection is employed, whole reduction process is safe and harmless.
(4) this method prepares graphene-based film based on spraying process, and reduction uses ultraviolet light, can suitably amplify progress
Engineering application.
(5) present invention efficiently, is simply prepared for the graphene-based function film from cleaning function, can be further by it
Applied to fields such as graphene-based conductive coating and graphene-based surface strain sensors.
Brief description of the drawings
Fig. 1 is the TEM figures that spraying prepares graphene oxide/titanium deoxid film；
Fig. 2 is the TEM figures that spraying prepares graphene oxide/titanium deoxid film；
Fig. 3 is the TEM figures that spraying prepares graphene oxide/carbon nano-tube/titanic oxide film；
Fig. 4 is the TEM figures that spraying prepares graphene oxide/carbon nano-tube/titanic oxide film；
Fig. 5 is the SEM figures that spraying prepares graphene oxide/carbon nano-tube/titanic oxide film；
Fig. 6 is the SEM figures that spraying prepares graphene oxide/carbon nano-tube/titanic oxide film.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Using ethanol as solvent, 0.2mg/ml graphene oxide solution, 0.5mg/ml titania solution are prepared.By two
Person is blended, and the mass ratio for making graphene oxide and titanium dioxide is 1: 1, ultrasonic 30min.Obtain graphene oxide and two
Titanium oxide dispersion liquid.6ml homogeneous solutions are taken to be added in spray gun.PC substrates are cleaned, then drying, is put on warm table
It is warming up to 100 DEG C.Now above-mentioned solution is injected on the PC substrates that area is 5 × 5cm using the spray gun for being associated with air pump, injection
Distance is 5cm or so.It is prepared for graphene oxide film/titanium deoxid film (as shown in Figure 1 and Figure 2).Film is stood on and is equipped with
200ml, concentration for 2mg/L methyl orange solution in carry out degradation experiment.Wherein the power of uviol lamp is 175W, and fluorescent tube is away from sample
Distance be 15cm, irradiation time is 10h.Sample after irradiation 10h is characterized, test result indicates that methyl orange solution
It has been degraded 12%.
Embodiment 2
Using ethanol as solvent, prepare 0.2mg/ml graphene oxide solution, add CNT make graphene oxide and
The mass ratio of CNT is 5: 1.Ultrasound 30min is then carried out, graphene oxide/CNT composite solution is prepared for.Together
Sample is prepared for 0.5mg/ml titania solution by solvent of ethanol solution.Three is blended, makes graphene oxide, carbon
The mass ratio of nanotube and titanium dioxide is 5: 1: 5, ultrasonic 10min.Obtain graphene oxide/carbon nano-tube/titanic oxide
Dispersion liquid.6ml homogeneous solutions are taken to be added in spray gun.PC substrates are cleaned, then drying, is put on warm table and is warming up to
100℃.Now above-mentioned solution is injected on the PC substrates that area is 5 × 5cm using the spray gun for being associated with air pump, jet length is
5cm or so.It is prepared for graphene oxide/carbon nano-tube/titanic oxide film (as shown in Fig. 3~Fig. 6).Film is stood on and is equipped with
200ml, concentration for 2mg/L methyl orange solution in carry out degradation experiment.Wherein the power of uviol lamp is 175W, and fluorescent tube is away from sample
Distance be 15cm, irradiation time is 10h.Sample after irradiation 10h is characterized, test result indicates that methyl orange solution quilt
Degrade 18%.Electrical performance testing is carried out after the completion of degraded to film, its square resistance is 100k Ω/sq.
Embodiment 3
Preparation method with the graphene-based film of self-cleaning function, comprises the following steps：
(1) graphene oxide dispersion is prepared in water/ethanol or ethanol solution, the concentration of graphene oxide is 0.1mg/
Ml, is prepared for dispersiveness and the preferable graphene oxide dispersion of stability after sonic oscillation.
It is preferred that, added with enhancing conductive material in graphene oxide dispersion, graphene oxide is led with enhancing
The weight ratio of electric material is 1: 1.It is CNT or metal nanometer line to strengthen conductive material.
(2) Nano titanium dioxide is added in ethanol solution, it is the two of 0.1mg/ml that concentration is prepared for after ultrasonic 1h
Titanium oxide dispersion liquid.
(3) by after graphene oxide dispersion and titanium oxide dispersion blending, appropriate ultrasound, obtain graphene oxide/
In titanium oxide dispersion, graphene oxide/titanium oxide dispersion, the weight ratio of graphene oxide and titanium dioxide is 1: 1.
(4) a certain amount of graphene oxide/titania solution dispersion liquid is taken to be added in the spray gun for being associated with air pump, in mesh
Sprayed on mark substrate, jet length is 5cm or so, uniformly prepares graphene oxide base film.
(5) prepared film is irradiated under ultraviolet light, fluorescent tube is 175W, the distance of fluorescent tube and sample is
15cm, irradiation time is 10h, and film is reduced, and is obtained with the graphene-based film of self-cleaning function.
Embodiment 4
Preparation method with the graphene-based film of self-cleaning function, comprises the following steps：
(1) graphene oxide dispersion is prepared in water/ethanol or ethanol solution, the concentration of graphene oxide is 2mg/
Ml, is prepared for dispersiveness and the preferable graphene oxide dispersion of stability after sonic oscillation.
It is preferred that, added with enhancing conductive material in graphene oxide dispersion, graphene oxide is led with enhancing
The weight ratio of electric material is 5: 1.It is CNT or metal nanometer line to strengthen conductive material.
(2) Nano titanium dioxide is added in ethanol solution, the dioxy that concentration is 1mg/ml is prepared for after ultrasonic 1h
Change titanium dispersion liquid.
(3) by after graphene oxide dispersion and titanium oxide dispersion blending, appropriate ultrasound, obtain graphene oxide/
In titanium oxide dispersion, graphene oxide/titanium oxide dispersion, the weight ratio of graphene oxide and titanium dioxide is 10:
1。
(4) a certain amount of graphene oxide/titania solution dispersion liquid is taken to be added in the spray gun for being associated with air pump, in mesh
Sprayed on mark substrate, uniformly prepare graphene oxide base film.
(5) prepared film is irradiated under ultraviolet light, fluorescent tube is 175W, the distance of fluorescent tube and sample is
15cm, irradiation time is 10h, and film is reduced, and is obtained with the graphene-based film of self-cleaning function.
Embodiment 5
Preparation method with the graphene-based film of self-cleaning function, comprises the following steps：
(1) graphene oxide dispersion is prepared in water/ethanol or ethanol solution, the concentration of graphene oxide is 1mg/
Ml, is prepared for dispersiveness and the preferable graphene oxide dispersion of stability after sonic oscillation.
It is preferred that, added with enhancing conductive material in graphene oxide dispersion, graphene oxide is led with enhancing
The weight ratio of electric material is 10: 1.It is CNT or metal nanometer line to strengthen conductive material.
(2) Nano titanium dioxide is added in ethanol solution, it is the two of 0.5mg/ml that concentration is prepared for after ultrasonic 1h
Titanium oxide dispersion liquid.
(3) by after graphene oxide dispersion and titanium oxide dispersion blending, appropriate ultrasound, obtain graphene oxide/
In titanium oxide dispersion, graphene oxide/titanium oxide dispersion, the weight ratio of graphene oxide and titanium dioxide is 20:
1。
(4) a certain amount of graphene oxide/titania solution dispersion liquid is taken to be added in the spray gun for being associated with air pump, in mesh
Sprayed on mark substrate, uniformly prepare graphene oxide base film.
(5) prepared film is irradiated under ultraviolet light, fluorescent tube is 175W, the distance of fluorescent tube and sample is
15cm, irradiation time is 10h, and film is reduced, and is obtained with the graphene-based film of self-cleaning function.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (4)
1. a kind of preparation method with the graphene-based film of self-cleaning function, it is characterised in that prepare graphene oxide respectively
Dispersion liquid and titanium oxide dispersion, and graphite oxide will be obtained after graphene oxide dispersion and titanium oxide dispersion blending
Alkene/titanium oxide dispersion, graphene oxide/titanium oxide dispersion is ejected into target base plate, graphene oxide is obtained
Base film；Ultraviolet light graphene oxide base film, is reduced to it, is obtained with the graphene-based film of self-cleaning function；
Added with enhancing conductive material in described graphene oxide dispersion, described enhancing conductive material for CNT or
Metal nanometer line；
In described graphene oxide dispersion, the weight ratio of graphene oxide and enhancing conductive material is 1:1~10:1；
The concentration of graphene oxide is 0.1~2mg/ml in described graphene oxide dispersion.
2. a kind of preparation method with the graphene-based film of self-cleaning function according to claim 1, it is characterised in that
The concentration of titanium dioxide is 0.1~1mg/ml in described titanium oxide dispersion.
3. a kind of preparation method with the graphene-based film of self-cleaning function according to claim 1, it is characterised in that
In described graphene oxide/titanium oxide dispersion, the weight ratio of graphene oxide and titanium dioxide is 1:1~20:1.
4. a kind of preparation method with the graphene-based film of self-cleaning function according to claim 1, it is characterised in that
Titanium dioxide used in preparing titanium dioxide dispersion liquid is Nano titanium dioxide.
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| CN106153621A (en) * | 2015-03-16 | 2016-11-23 | 北京中清国研环境技术研究院 | A kind of water quality monitoring automatically cleaning film sensors |
| CN104877572A (en) * | 2015-04-20 | 2015-09-02 | 青岛瑞利特新材料科技有限公司 | Graphene additive and application thereof in shoe cream |
| CN109423068A (en) * | 2017-06-23 | 2019-03-05 | 北京国信优控***技术有限公司 | Super-hydrophobic wear-resisting graphene composite coating and the solar energy heat collection pipe for applying it |
| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
| CN107537320A (en) * | 2017-08-25 | 2018-01-05 | 杭州高瓴环境科技有限公司 | A kind of composite membrane and preparation method thereof |
| CN108043379A (en) * | 2017-12-11 | 2018-05-18 | 河南师范大学 | Graphene/TiO2Composite and flexible photocatalysis membrana and preparation method thereof |
| CN108754460A (en) * | 2018-05-18 | 2018-11-06 | 蚌埠心里程电子科技有限公司 | A kind of Metal surface anti-corrosion automatically cleaning processing method |
| CN108722206B (en) * | 2018-07-04 | 2020-10-30 | 同济大学 | Anti-pollution self-cleaning GO/ZnO-PVDF film and preparation method thereof |
| CN113694915A (en) * | 2021-08-25 | 2021-11-26 | 特灵空调***(中国)有限公司 | Preparation method of titanium dioxide/graphene composite material |
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| CN102700185A (en) * | 2012-05-25 | 2012-10-03 | 清华大学 | Preparation method of graphene oxide/titanium oxide layered composite film |
| CN104001504B (en) * | 2014-05-13 | 2016-10-05 | 河海大学 | Silver and the co-modified TiO of Graphene2the preparation method of nano wire and the effect of photocatalysis degradation of pollutants in waste water |
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