CN104591162B - Preparation method of multi-response graphene/graphite oxide film - Google Patents
Preparation method of multi-response graphene/graphite oxide film Download PDFInfo
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- CN104591162B CN104591162B CN201410817909.6A CN201410817909A CN104591162B CN 104591162 B CN104591162 B CN 104591162B CN 201410817909 A CN201410817909 A CN 201410817909A CN 104591162 B CN104591162 B CN 104591162B
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- graphite oxide
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Abstract
The invention relates to a preparation method of a multi-response graphene/graphite oxide film. The method comprises the following steps of: ultrasonically dispersing the graphite oxide in deionized water to obtain a graphite oxide aqueous solution, and then, regulating the pH value to 2-6 by using acid; placing an active metal plate in the graphite oxide aqueous solution, placing the graphite oxide aqueous solution on a horizontal platform and maintaining temperature of 10-15 DEG C, standing, taking out the active metal plate 1-7 days later, washing, drying, and peeling off the film, then, thereby obtaining the multi-response graphene/graphite oxide film. The preparation method provided by the invention is simple, and can implement large-scale and low-cost production.
Description
Technical field
The invention belongs to the preparation field of multiple response material, particularly to the Graphene/graphite oxide thin film of a kind of multiple response
Preparation method.
Background technology
Stimulating deformable material is that its shape can be according to stimulation under by external environment stimulation (such as light, temperature, humidity etc.) for a class
Degree and there is the material changed in various degree.Common actuator is shaped with electrostatically actuated, piezoelectric actuated, Electromagnetically actuated, shape
Shape memory alloys actuating, light actuating and thermal actuation etc..In recent years its as a kind of artificial intelligence's material increasingly by research work
The concern of person, particularly shows great application prospect in fields such as artificial-muscle, CD-ROM driver and Miniature optical mechanical systems.
Compared with other activation manners, light (temperature) activates has remote-controlled energy supply, and without wire, driving force is big, and deflection is big, light
Driving cleaning, safety, not by advantages such as electromagnetic interference, therefore the stimulation deformable material of light (temperature) activating profile is considered as
One of potential actuating material.The most this deformable material is with the cross-linking type liquid crystal high score containing photosensitive groups such as diphenyl diimides
Son is the material of most study, and the deformation of material is realized by the photoisomerization of azobenzene group.Current this material exists
Multiple optical drive flexible device is applied, such as plastics motor, Flexible Miniature Robotic, high frequency generator, staple fibre etc..
But this kind of optical drive deformable material is usually present some problems, such as macromolecular orientation complex process, photoresponse in preparation process
Time length (> 10s), the problems such as regeneration rate is slow, repeatable accuracy the highest (5%～20%), significantly limit it performance and
Application.
From Univ Manchester UK physicist An Deliehaimu (Andre Geim) in 2004 and Constantine's Nuo Woxiao love
(Konstantin Novoselov), isolates Graphene the most in an experiment from graphite, and confirms that it can be with individualism by extensively
General concern and research.Owing to having the most excellent optics, the performance such as electrochemistry and machinery its be applied in a lot of fields,
Including nanometer electronic device, supercomputer, solaode, photon sensor and gene sequencing etc..
Summary of the invention
The technical problem to be solved is to provide the preparation method of the Graphene/graphite oxide thin film of a kind of multiple response, this
Inventive method preparation is simple, can realize extensive, low-cost production.
A kind of preparation method of the Graphene of the multiple response of the present invention/graphite oxide thin film, including:
(1) by the method for chemical stripping, crystalline flake graphite is prepared as graphite oxide；
(2) by graphite oxide ultrasonic disperse in deionized water, obtain graphite oxide aqueous solution, be then 2-6 with acid for adjusting pH；
(3) work ripple metallic plate is placed in graphite oxide aqueous solution, places levelling bench and keep temperature to be 10-50 DEG C, place 1-7
My god, take out ripple metallic plate afterflush of living, be dried, stripping film, obtain the Graphene/graphite oxide thin film of multiple response.
In described step (2), the concentration of graphite oxide aqueous solution is 1mg/ml～15mg/ml.
In described step (2), acid is the one in sulphuric acid, hydrochloric acid.
Ripple metallic plate of living in described step (3) is the one in Copper Foil, nickel foil, steel plate；Live the most ultrasonic place of ripple metallic plate
Reason.
Described organic solvent is one or more in ethanol, acetone.
Ripple metallic plate of living in described step (3) is placed in graphite oxide aqueous solution, and metallic plate is 5cm～25cm away from liquid level.
Described step (3) is rinsed for deionized water rinsing；50 DEG C of drying baker are dried as 3-8h.
The Graphene of the multiple response obtained in described step (3)/graphite oxide thin film issues change at illumination, steam, thermal stimulus
Shape, removes and restores to the original state after stimulating.
(as a example by Copper Foil), the redox reaction that wherein surface, active metal occurs is:
NCu+nGO+2n H+=nCu2++nrGO+nH2O。
Active metal sheet material substrate, in acid condition can be anti-with the oxidized graphite flake layer generation oxidoreduction being adsorbed onto its surface
Should, make graphite oxide be reduced to a certain extent, and the graphite oxide reducing degree the most first adsorbed is the biggest.
The reversible multiple stimulation that the present invention provides drives the preparation method of deformable membrane, with active metal as reducing agent, with chemical method
Graphite oxide prepared by stripping method is raw material, be prepared for by the way of liquid deposition reversible multiple stimulation drive deformation Graphene/
Graphene oxide film.
Chemical method of the present invention prepares the step of graphite oxide: joined by natural flake graphite in the concentrated sulfuric acid solution of potassium permanganate,
And stir 2 hours in ice-water bath (～0 DEG C), then move in 98 DEG C of oil bath pans and add 200mL deionized water, insulation
By reactant filtering and washing after 0.5 hour, obtain graphite oxide prepared by chemical method.
The present invention makes two kinds of compositions different structure and row occur by special reduction means and thin film-forming method on same thin film
Cloth, thus show the effect that multiple environmental stimuli (illumination, steam and temperature) is had deformation response, two kinds simultaneously
Composition does not has sharp interface to be i.e. to be another kind of composition by a kind of composition gradually transition, prepared thin film need not to add any
Under illumination, steam and thermal stimulus, there is fast deformation in the case of traditional Photo alignment is high molecular, remove meeting after stimulating
Restore to the original state, and significantly do not decay and tired, simultaneously with active metal substrate liquid phase layer by layer from group after repeating up to a hundred times
The method of dress also gives the preferable mechanical property of this material and electric property.
The method of the liquid deposition used by the present invention can control different time well and deposit to the graphite oxide on surface, active metal
There is different reducing degrees, so that the thin film upper and lower surface of preparation has different character i.e. with the one side of metal-clad also
Originality is higher has good photothermal deformation ability, and another side is substantially at non-reducing condition and has preferable Vapor adsorption Desorption Energy
Power, this is also to realize stimulating driving the basic of deformation.
Multiple stimulation prepared by the inventive method drives deformable membrane material can stimulate light, steam and temperature etc. and makes deformation
Behavior.When light beam is irradiated to film surface, it can make the action to graphite oxide one side bending, keeps irradiation distance and merit
Rate not variation film maintains deformation state constant, stops irradiating thin film and quickly recovers to flattened state；For temperature, there is same effect
Really.For the stimulation of steam, steam blows to film surface, and it can be made to the bending of reduced graphene film side, stops blowing
Thin film then recovers smooth.Deformation under three of the above stimulates all can repeat up to a hundred times and occur without significantly decay.
The reversible multiple stimulation of one prepared by this method drives in deformation Graphene/graphite oxide thin film due in liquid phase environment
The time of graphite oxide deposition is different and makes two surfaces have bigger reducing degree difference；Sedimentation time and character simultaneously
Difference result also in two parts of thin film and has bigger architectural difference, and Graphene side has closely knit interlayer structure and aoxidizes stone
Ink side has loose three-dimensional net structure；The graphite oxide utilizing reducing degree higher has higher photo-thermal conversion efficiency,
The graphite oxide that oxygen-containing functional group is more simultaneously has the absorption stronger to steam and desorption ability (along with the change of surface temperature)；
The combination of both character makes thin film have following characteristics: fast deformation occurs under illumination, steam and thermal stimulus, removes thorn
Can restore to the original state after Jiing, and there is preferable fatigue durability.
In sum, the present invention proposes the preparation of a kind of Graphene/graphite oxide thin film possessing the driving deformation of reversible multiple stimulation
Method, this method by special reduction means and film build method make on same thin film two kinds of compositions occur different structure and
Arrangement, thus show the effect that multiple environmental stimuli (illumination, steam and temperature) is had deformation response.This thin film
Can be widely used in driving field of functional materials, be that a kind of high-performance of preparing activates the universality method of thin film.
Beneficial effect
The reducing degree controlling graphite oxide that the present invention is artificial during preparing thin film and the oxidation of its different reducing degrees
The spatial distribution (thin film one side is the Graphene that reducing degree is higher, and another side is the graphite oxide that oxygen-containing functional group is more) of graphite.
Combining high photo-thermal conversion efficiency and graphite oxide adsorption/desorption preferable to the steam ability of Graphene, appointing need not add
Achieve it in the case of what Photo alignment high score subclass material and fast deformation occurs under illumination, steam and thermal stimulus, go
Except restoring to the original state after stimulating, and there is preferable fatigue durability.Preparation method of the present invention is simple, it is possible to achieve extensive, low
Cost produces.
Accompanying drawing explanation
Fig. 1 is the detailed process schematic diagram of the Graphene/graphite oxide thin film of embodiment 1 preparation；
The field emission scanning electron microscope photo of thin film prepared by Fig. 2 embodiment 1, wherein a is the Electronic Speculum figure of whole thin-membrane section；B is thin
The high multiple Electronic Speculum figure of film upper surface (graphene oxide side)；C is the high multiple electricity of thin film lower surface (Graphene side)
Mirror figure；
Fig. 3 is the upper and lower surface Raman Characterization that embodiment 1 prepares thin film；
Fig. 4 is the Graphene/graphite oxide thin film of present invention optical drive deformation under 1000nm infrared light；
Fig. 5 is the Graphene/graphite oxide thin film deformation under steam of the present invention；Wherein, I-VIII is tumbling state.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
Concentration in deionized water is disperseed to be 1mg/ml the graphite oxide that height is peeled off, ultrasonic after dropping sulfur acid for adjusting pH to 2
Dispersion obtains the graphite oxide aqueous solution having good stability.After required copper coin organic solvent (ethanol or acetone) ultrasonic cleaning
Dry and be placed in (distance liquid level 10cm) bottom the glass drying oven equipped with the previously graphite oxide aqueous solution of configuration.Glass drying oven is quiet
Being placed in levelling bench upper 1 day and to keep temperature be 20 DEG C, copper coin bottom taking-up, now copper coin surface is deposited a layer graphene
/ graphite oxide hydrogel, puts into copper coin to be dried in the drying baker of 25 DEG C 6 hours and takes out, peeled off by thin film subsequently from copper coin.
Fig. 2 is the field emission scanning electron microscope figure of Graphene/graphite oxide thin cross-sections prepared by this method, can be clear from Fig. 2 a
The structure seeing whole section be not homogeneous, its section be a compact structure from below be gradually transitions top dredge
Loose structure, from Fig. 2 b of higher multiple, is more clearly seen in weaker zone the hole with some three-dimensionals in c.
Character by upper and lower two surfaces of Raman spectrum analysis thin film.Fig. 3 is Raman spectrum analysis result, is drawn by individual surface
The contrast of graceful spectrum is it can be seen that intensity contrast I at thin film lower surface (one side contacted with metal basal board) its D peak and G peakD/IG
(lower surface I bigger than upper surfaceD/IG=1.28, lower surface ID/IG=1.09) thin film lower surface, is sufficiently demonstrated by active metal
Reduction, upper surface is then in graphite oxide state.Different from traditional Two-phase composite structure, the present invention is sunk by a step liquid phase
Area method is prepared for two-phase coexistent but the multiple stimulation of substantially boundary activates the thin film of response, have well activate response and
Structural stability.
Fig. 4 is that thin film was made in 0.33 second at the radiation of visible light thin film that 560 nanometers, intensity are 50 milliwatts/square centimeter
Bending response, removes illumination thin film and returned to formation state in 3.67 seconds, and whole process shows higher response speed with extensive
Complex velocity.Graphene/graphite oxide the thin film prepared by the present invention has higher mechanical strength, and (fracture strength is up to
473MPa), reduction mask has higher conductivity (5000S/m) simultaneously, and higher mechanical strength and good conductivity make
It can be distinguished traditional high-molecular optical completely and cause deformable material, can significantly widen its application.
Embodiment 2
Concentration in deionized water is disperseed to be 5mg/ml the graphite oxide that height is peeled off, ultrasonic after dropping sulfur acid for adjusting pH to 4
Dispersion obtains the graphite oxide aqueous solution having good stability.After required copper coin organic solvent (ethanol or acetone) ultrasonic cleaning
Dry and be placed in (distance liquid level 10cm) bottom the glass drying oven equipped with the previously graphite oxide aqueous solution of configuration.Glass drying oven is quiet
Putting and levelling bench upper 1 day to keep temperature be 30 DEG C, copper coin bottom taking-up, now copper coin surface is deposited a layer graphene
/ graphite oxide hydrogel, puts into copper coin to be dried in the drying baker of 50 DEG C 2 hours and takes out, peeled off by thin film subsequently from copper coin.
The thin film taken off is formation state, places it on the permeable non-woven fabrics of steam the hot water of 80 DEG C (lower section be), thin film table
Reveal tumbling state (such as Fig. 5), and the sustainable long period and occur without decay situation.
Claims (6)
1. a preparation method for the Graphene of multiple response/graphite oxide thin film, including:
(1) by the method for chemical stripping, crystalline flake graphite is prepared as graphite oxide；
(2) by graphite oxide ultrasonic disperse in deionized water, obtain graphite oxide aqueous solution, be then 2-6 with acid for adjusting pH；
Wherein the concentration of graphite oxide aqueous solution is 1mg/ml～15mg/ml；
(3) work ripple metallic plate is placed in graphite oxide aqueous solution, places levelling bench and keep temperature to be 10-50 DEG C, place 1-7
My god, take out ripple metallic plate afterflush of living, be dried, stripping film, obtain the Graphene/graphite oxide thin film of multiple response；
Ripple metallic plate of wherein living is placed in graphite oxide aqueous solution, and metallic plate is 5cm～25cm away from liquid level.
The preparation method of the Graphene of a kind of multiple response the most according to claim 1/graphite oxide thin film, it is characterised in that:
In described step (2), acid is the one in sulphuric acid, hydrochloric acid.
The preparation method of the Graphene of a kind of multiple response the most according to claim 1/graphite oxide thin film, it is characterised in that:
Ripple metallic plate of living in described step (3) is the one in Copper Foil, nickel foil, steel plate；Ripple metallic plate of living surpasses in organic solvent
Sonication.
The preparation method of the Graphene of a kind of multiple response the most according to claim 3/graphite oxide thin film, it is characterised in that:
Described organic solvent is one or more in ethanol, acetone.
The preparation method of the Graphene of a kind of multiple response the most according to claim 1/graphite oxide thin film, it is characterised in that:
Described step (3) is rinsed for deionized water rinsing；Put into and 50 DEG C of drying baker are dried 3-8h.
The preparation method of the Graphene of a kind of multiple response the most according to claim 1/graphite oxide thin film, it is characterised in that:
The Graphene of the multiple response obtained in described step (3)/graphite oxide thin film occurs under illumination, steam, thermal stimulus
Deformation, removes and restores to the original state after stimulating.
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| CN106587016A (en) * | 2016-12-08 | 2017-04-26 | 南京信息职业技术学院 | Oxidized graphene humidity response actuator and preparation method thereof |
| CN107201996B (en) * | 2017-06-07 | 2019-08-27 | 中国科学技术大学 | The preparation method of photic dynamic laminated film, photic dynamic laminated film and optical actuator |
| CN107684834B (en) * | 2017-09-19 | 2020-11-24 | 北京航空航天大学 | Intelligent response type graphene-based separation membrane for mixed molecular separation and preparation method thereof |
| CN108356809A (en) * | 2018-02-09 | 2018-08-03 | 浙江工业大学 | A kind of origami structure based on optical drive autofolding |
| CN108358198A (en) * | 2018-03-07 | 2018-08-03 | 中国工程物理研究院化工材料研究所 | Multiple environment response driving graphene oxide film, preparation method and application |
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