CN104039695B - Redox graphene and its production method - Google Patents
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- CN104039695B CN104039695B CN201280056867.8A CN201280056867A CN104039695B CN 104039695 B CN104039695 B CN 104039695B CN 201280056867 A CN201280056867 A CN 201280056867A CN 104039695 B CN104039695 B CN 104039695B
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Abstract
The present invention provides a kind of method for producing reduction (rGO) or partial reduction (prGO) graphene oxide membrane, which has the electrical conductivity of improvement.This method can generate highly conductive (2000S/cm), flexible, printable, machinable redox graphene material, without harsh chemical treatment or high annealing.In one embodiment, the circuit being made of redox graphene trace can be printed to by using the preferred ascorbic acid of reducing agent in graphene oxide membrane.
Description
Technical field
The present invention relates to a kind of methods for the graphene oxide for producing reduction and/or partial reduction.
Background technology
Grapheme material provides highest known conductivity for single-layer system.Therefore, it is contemplated that graphene and class graphene
Material will be as the main material of next-generation electronic equipment.
Graphene is generally produced by mechanical stripping method or chemical vapor deposition (CVD) method.Although these methods can give birth to
High-crystallinity High conductivity graphene is produced, but for large-scale production, they usually can not scale or not cost-effective.
Another method is electronation graphene oxide (GO), is easily produced by graphite.It however, although can phase
To relatively easily producing graphene oxide composite material, but subsequently the reducing process of class grapheme material can only obtain so far compared with
The electrical conductivity (~10-100S/cm) of difference, with the electrical conductivity of pure graphene (>3000S/cm) differ greatly.Product one through reduction
As be known as redox graphene (rGO or reGO).Using the redox graphene (rGO) of existing method production and part also
Former graphene oxide (prGO) is similar to graphene in terms of lattice structure, but has the defects of residual oxygen and configuration aspects.Phase
For graphene, these defects significantly reduce the electrical conductivity of report.But electrical conductivity and that of doping conducting polymer and silicon
It is a little suitable.
Post processing or high annealing can make electrical conductivity be up to 500-700S/cm, but such treatment conditions are in semiconductor
It is infeasible in industry, and without large-scale commercial applications feasibility.
Up to the present, had been reported in the literature by the various chemical reduction methods of a large amount of GO materials production rGO.Example
Such as, by the way that GO thin slices are immersed in hydrazine, exposed to the combination life of hydrazine steam, electrochemical reduction, thermal annealing and these technologies
The graphene that output chemical method obtains.Most common chemistry route is by using hydrazine, toxicity reducing agent and subsequent height
Temperature annealing.But the rGO films produced by these methods are limited in terms of exploitation, and the rGO electrical conductivity up to the present obtained
It is low, internal resistance is high.
Another method is to carry out adjustable reduction to GO by the resistance heating of AFM cantilevers.But, this method is not suitable for
For large-scale commercial applications production technology.
Graphene oxide (GO) sill is potential in application in extensive range, including storage device, sensing platform,
Cell culture, electrochemical energy source device, high sensitive gas sensor and the factor of quality are more than the mechanical resonator of graphene resonator.
The band gap at room temperature of GO is more than 0.5eV, while has localization semiconductor and semimetal characteristic, this is because it is towards class graphene
Material direction is reduced.
The present invention attempt to provide in one simply can scale and ecological sustainability chemical method, with the high electricity of production
Conductance (~2000S/cm), flexible, printable, machinable redox graphene material, at harsh chemistry
Reason or high annealing.
The content of the invention
In a kind of broad form (form) of the present invention, a kind of oxidation for producing reduction or partial reduction is provided
The method of graphene, the method comprising the steps of：
(a) graphene oxide is provided；With
(b) reducing agent is added at least part graphene oxide.
In further form, step (a) includes providing matrix, and described matrix surface includes graphene oxide.
In further form, the matrix surface of step (a) includes graphene oxide layer.
In further form, the graphene oxide layer of reduction or partial reduction is generated on the surface.
In further form, reducing agent is applied selectively in graphene oxide layer so that reduction or part are also
Former graphene oxide forms a pattern (pattern) in graphene oxide layer.
In further form, step (a) includes for graphene oxide dispersion being coated or deposited on the surface of matrix
On.
In one form, the dispersion of graphene oxide includes dispersion graphene oxide in water.
In another form, the reducing agent of step (b) applies as a part for solution.
In further form, step (b) includes to include the matrix surface immersion of graphene oxide or dip-coating in bag
In solution containing reducing agent.
In one form, step (b) includes the solution comprising reducing agent being printed onto the matrix comprising graphene oxide
On.
In one form, printing includes intaglio printing, roll-to-roll (roll-to-roll) printing, reel-to-reel
(reel-to-reel) printing, inkjet printing or flexographic printing.
In further form, the solution comprising reducing agent is aqueous solution.
In one form, the reducing agent of application is ascorbic acid.
In another form, between the electrical conductivity of the graphene oxide of reduction or partial reduction is about 0-5000S/cm.
In further form, graphene oxide composite materials layer is included on the matrix surface of step (a).
In further form, the present invention provides included on the surface produced according to any one of above-mentioned form
The matrix of the graphene oxide of reduction or partial reduction.
In one form, the form of the graphene oxide of reduction or partial reduction is circuit pattern (circuit
pattern)。
In one form, the present invention provides what is produced according to any one of above-mentioned form to include reduction or part
The equipment (device) of the graphene oxide of reduction.
In one form, the present invention provides the graphene oxide layers in its surface with reduction or partial reduction
Matrix, the thickness of this layer are less than 2 μm, and electrical conductivity is more than 1000S/cm.
In one form, the present invention provides the reduction or part produced according to any one of above-mentioned form method
Purposes of the graphene oxide of reduction as conductive or partially electronically conductive coating, antimicrobial coating, corrosion-inhibiting coating or antistatic coating.
In one form, the present invention provides the reduction or part produced according to any one of above-mentioned form method
The graphene oxide of reduction is as conductor for the purposes of the electrical conduction of electric power.
Description of the drawings
Below with reference to the accompanying drawings, the various non-limiting embodiments of the present invention are described in detail, the present invention will become more
It is readily appreciated that, wherein：
Fig. 1 shows the rGO traces (track) generated using conventional ink jet printers in GO films；
Fig. 2 shows the rGO layers of different-thickness；
Fig. 3 a are the X ray diffracting spectrums of natural GO, reGOl, 2 and 3；
Fig. 3 b are the Raman spectrums obtained in 633nm, it is shown that D, G, 2D and G of spectrum ' regions (2D in illustration-spectrum
And G ' regions more detailed view)；
Fig. 3 c are the x-ray photoelectron spectroscopies in the C1 regions of GO；
Fig. 3 d are the x-ray photoelectron spectroscopies in the C1 regions of reGO1；
Fig. 3 e are the x-ray photoelectron spectroscopies in the C1 regions of reGO3；
Fig. 4 a show the flexible interlayer type pair using the poly- difluoroethylenes of flexible rGO/ (PVDF) prepared /rGO films assembling
Claim capacitor battery, both sides there are the rGO films of identical size (mass weight is each 0.456mg)；
Fig. 4 b show the constant current charge-discharge rate of the capacitor in Fig. 4 a；
Fig. 4 c are the SEM images of the rGO films comprising Pt nanoparticle；
Fig. 4 d are the linear sweep voltammetry figures of the rGO films comprising Pt nanoparticle；
Fig. 4 e show the partial reduction rGO films on PET sheet/glass of ITO coatings；
Fig. 4 f are the differential pulse voltammetry DPV carried out to partial reduction GO surfaces, with the dopamine of detection deposition；
Fig. 5 is the transmission electron microscope image of GO before reduction；
Fig. 6 is the scanning electron microscope image of GO before reduction；
Fig. 7 a show the rGO circuits for lifting the ink-jet impression on preceding glass slide on GO；
Fig. 7 b show the rGO circuits for lifting independent Fig. 7 a after adhesive tape；
Fig. 8 shows the reality that the adhesive tape of GO/RGO is lifted to formed independent circuits and equipment from glass slide
Example；
Fig. 9 a, which are shown, lifts the preceding patterned RGO dipoles RFID label tag by inkjet printing on glass for having adhesive tape
Design；
Fig. 9 b show after adhesive tape is lifted as autonomous device Fig. 9 a RFID label tag；
Figure 10 a show the GO for being covered in the RGO patterns with 10x10mm conversions on ito glass；
Figure 10 b show that adhesive tape starts the RGO of Figure 10 a left after GO；
Figure 11 a show the ink-jet impression RGO circuits in the GO on ito glass matrix；And
Figure 11 b show that the ink-jet impression RGO that Figure 11 a after GO are removed with adhesive tape, the LED of surface installation are attached with
Aluminium paint.
Specific embodiment
The description of front is only some embodiments of the present invention, in the case of without departing substantially from scope and spirit of the present invention
It can be modified and/or changed, these embodiments are illustrative, and nonrestrictive.
In the context of the present specification, word "comprising" refer to " contain substantially but need not uniquely contain " or " having " or
" containing " rather than " only by ... form ".The deformation of word " include (comprising) ", for example, " including (comprise) " and
" including (comprises) " has the corresponding various meanings.
Some embodiments provide a kind of side for producing reduction (rGO) or partial reduction (prGO) graphene oxide membrane
Method, the film have the electrical conductivity improved compared to the rGO films prepared with other methods.
In addition, the method for the present invention can with use environment friendly and easy scale process selectivity redox graphene
(GO) film.
The method that the present invention describes by the GO being deposited on matrix reduce rather than chemical reducing solution in GO and with
RGO is coated to surface afterwards.The new application that inventor illustrates the improvement and specific reductant to processing sequence is aobvious to show
Write advantage.Advantageously, in the methods of the invention, GO films can use reducing agent impression or printing, high to be produced in GO dielectric substrates
Spend conductive rGO traces.
The advantages of method described herein, includes：
- the electrical conductivity measured is close to the electrical conductivity (~3000S/cm) of the pure CVD graphenes generated
- need not high temperature or post processor.In general, this method can be implemented at ambient temperature.This is in such as electronics
Industry is an important factor, because back-end chip technology requirement program temperature is less than 300 DEG C.
- can be with the friendly reducing agent of use environment and operation, such as ascorbic acid.
In certain embodiments, the matrix that graphene oxide is deposited on is prepared during beginning.With graphene oxide
Matrix can be prepared differently.In general, the paddle dispersion of GO is prepared first.GO dispersions may include GO in water, second
Dispersion in alcohol, ionic liquid, solvent or other liquid-carriers.Liquid-carrier may include glycol ether, for example, diethylene glycol
Monobutyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol n-butyl ether acetate or ethylene glycol monobutyl ether.
Wt% graphene oxides in graphene oxide dispersion are variable, and generally be selected to be suitble to GO or with
The final application of the rGO materials generated afterwards.For example, graphene oxide dispersion can include low (be less than 0.5wt%), in
The graphene oxide of (0.5wt% is between 2.0wt%) and high (being more than 2wt%) concentration.
GO dispersions can further comprise following any one or combination：Biological reagent, enzyme, cell, polymer, fibre
Dimension, ionic liquid, nano material (such as nano particle, nanotube, nanometer sheet and nanometer rods) and/or other active precursor (examples
Such as monomer, AgNO3、AuCl3And H2PtCl6And other metal salts).
Once preparing, then paddle GO dispersions can be deposited on the surface of matrix.Painting in extensive range can be used
Cover/deposition technique deposits GO, including cutter painting, spraying (such as air spraying), inkjet printing, silk screen printing, spin coating, droplet casting,
Dip-coating, brushing, intaglio printing, flexographic printing, blade coating, metering bar coating, channel mould coating etc..Filtering, Langmuir-
Blodgett, electrospinning or fibre spinning.
It will be appreciated by those skilled in the art that base material can be rigidity, flexibility or soft.For example, matrix may include film, by gold
Category, polymer, film, glass, silicon, other coatings and even multilayer made of crystal or 3D structures.For example, matrix can be with
It is glass slide, solid metal piece, metal or Metal Substrate paper tinsel (such as copper foil or aluminium foil), plastic sheet (such as PET or Au-Mylar), thin
Film (such as PVDF), paper, the matrix of polymer matrix, rubber, polymer gel, hydrogel, SPE films, crosslinking SPE, fabric are (such as
Cloth), fine fabrics (such as Kevlar or Gortex) or next-generation fiber (such as graphene oxide fiber).
It will be appreciated by those skilled in the art that matrix surface can include GO composite materials.
In addition, a part for the compound GO materials of act or omission, matrix surface can include biological reagent, enzyme, cell, poly-
Close object, fiber, ionic liquid, nano material, nano particle, nanotube, nanometer sheet, nanometer rods, active precursor, monomer,
AgNO3、AuCl3And H2PtCl6And any one of other metal salts or combination.
To obtain rGO or prGO, as required, reducing agent is added in the GO on matrix.Reducing agent is usually solution
A part.Solution comprising reducing agent can be aqueous solution, organic solution or ionic liquid.Solution may include glycol ether, example
Such as, diethylene glycol monobutyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol n-butyl ether acetate or ethylene glycol monobutyl ether.
Reducing agent can be inorganic or organic.For example, reducing agent can include ascorbic acid, oxalic acid (C2H2O4), formic acid
(HCOOH), sodium borohydride (NaBH4), cell, lithium aluminium hydride (LiAlH4), sulfite compound, phosphite, phosphorous acid or
Citric acid.Reducing agent can also be electroactive polymer.
Ascorbic acid is naturally occurring compound, and aqueous solution can be used as to provide, environmental-friendly so as to provide one
Reducing agent.
GO reduced levels and thus obtained synthesis rGO electrical conductivity can be by changing concentration, the class of reducing agent of reducing agent
Type, temperature and GO are controlled exposed to the time of reducing agent.Optionally apply reducing agent to be provided in insulation GO Medium Cultures
Conductive rGO patterns.
The various technologies of including but not limited to dip-coating or printing can be used to apply reducing agent.Printing include intaglio printing,
Roll-to-roll printing, reel-to-reel printing, inkjet printing or flexographic printing.Gas phase impression (vapour phase can also be used
Patterning) reducing agent is applied.
Fig. 1, which is shown, reduces the selection area that GO films carry out using the conventional ink jet printers for being loaded with reducing agent.Herein
In embodiment, characteristic size is limited be subject to inkjet nozzle, but this method can a series of components of step printing.Fig. 1 is shown
Ball bearing made show rGO traces, sheet resistance is 200 Ω/, by inkjet printing into the pattern in GO films.When using
During inkjet printing, by adjusting drop size and the drying time of reducing agent, the rGO traces generated in GO films can be further adjusted
Electrical conductivity.
The rectangular patterns that Fig. 2 is shown show the different resistivity structure produced according to the method for the present invention.By changing also
The number of former agent type channel or the layer of coating, can obtain different resistivity.From the left side, rectangle represents 120 Κ Ω respectively
(1 passage), 13 Κ Ω (2 passage), 2 Κ Ω (5 passage), 600 Ω (10 passage), the resistivity of 200 Ω/sq (15 passage).
The thickness of reduction or partial reduction graphene oxide layer can be different according to required application.
For 3D equipment applications, it can then apply reducing agent in the coat of GO of substrate deposit " paper " a series of.With
Each layer of deposition also can apply structural fixation/bonding agent to the GO not reduced.This can be in the GO Medium Cultures of high-insulation
Generate highly conductive 3D rGO equipment.These matrix can be such as exhausted for stable structure potentially through mechanical processing to produce
(for example, the loud speaker of all size ranges, from earphone to large scale loud speaker, electromagnet starts sensing apparatus in edge platform
Machine, transformer etc.) without metal solid air core coil or metal core coil and helix tube.Alternatively, rGO " paper " itself can be successively
It deposits or for this process, previously prepared " paper " of customized thickness can be used.
It is lifted in addition, having developed an easy selectivity except technique (lift-off process), figuratum rGO will be printed
Feature is removed from matrix, to form flexible independent rGO structures and equipment.The technique generally requires one piece of adhesive tape, glues
It is placed under closing laterally on the GO/rGO surfaces of generation.Then adhesive tape is carefully started from support substrate.During lifting and removing, base
The surface energy of body determines the degree that rGO is removed.Unconverted GO regions can also be selectively removed, rGO patterns are stayed in
Matrix surface.
Coated GO relative hydropathics and rGO is relatively hydrophobic.Therefore, when rGO conversion pattern when on hydrophobic surface, bonding
Power, which is enough to resist adhesive tape to lift, to be removed.On less hydrophobic matrix such as glass, rGO will be removed together with the GO regions of surrounding.
In this case, second piece of adhesive tape can be used to be laminated the adhesive tape started, protect rGO patterns and formed flexible only
Vertical pattern.
The embodiment for lifting divided by producing autonomous device from glass slide is shown in figures 7-9.It is coated from more hydrophobic ITO
Unconverted GO materials are selectively removed on glass to show in figures 10 and 11.
For the embodiment of Figure 11, generate thereon the ITO coatings of rGO patterns glass scraped off to be formed two it is discrete
Contact block.LED is attached on the rGO of every piece of discrete contact block.Contact with LED passes through the conductive electricity of ITO from below
The rGO engagement pads of pole are realized.
It should also be understood that reducing agent can also assign the other properties of rGO layers of generation.Reducing agent can simultaneously be used as reducing agent and
The component of compound rGO materials after reduction.
For example, acidity electroactive conductive polymers can be used as reducing agent.This polymer reduces GO in acidity.It removes
Reduction, polymer also provide electroactive properties (for example, can between conduction and state of insulation reversible transformation) for rGO.
The RFID label tag of Fig. 9 is prepared by printing water-soluble electroactive conductive polymers.
Therefore the method for the present invention can provide the method that 1 step manufactures rGO/ equipment complexes by printing function reducing agent, and
RGO patterns need not be initially formed, then chromatography functional material completes equipment.
In addition, this 1 one step process can form the 3D networks of two kinds of materials, and multistep method shape on the surface of rGO patterns
Into polymer film.
As described, inventor is it has been shown that prepare highly conductive (~2000S/cm) redox graphene structure can
It adjusts, expansible, continuity of environment chemical method, without harsh chemical processing or annealing.
The present invention can also by it is a kind of it is expansible in a manner of in preformed graphene oxide structure generate different electricity
The pattern of resistance rate.Generation is can control by changing parameter such as reductant concentration, reducing agent or temperature, those skilled in the art
The resistivity that rGO is obtained.The method of the present invention can obtain the sheet resistivity down to 2Ohm/sq.Such resistivity, which is equivalent to, to be connect
The resistivity of the graphene of nearly CVD generations.In addition, the reducing agent applied in method can pass through inkjet printing so that can use one
It walks program and generates electric circuit construction.
These structures show the unprecedented control to redox graphene property, so as to obtain class graphene
Electrical conductivity.This control can realize virtually limitless process choice, and the selection is suitable for a series of typography, such as
Ink-jet, roll-to-roll and reel are to reel technology.
Method described herein provides the next-generation redox graphene of production a batch using the chance with equipment.Example
Such as, method of the invention can be used for production electrode, sensor, bionical equipment, energy conversion, fuel cell, solar-electricity
Pond, moisture electrolytic cell, water cleaning battery, energy storage devices, rechargeable battery, ultracapacitor, hybrid battery, electronics are set
Standby, display device, electrochromism battery, exchange/assets tracing equipment, passive or active RFID tag, electrochemical apparatus and/or
Wearable device.
Other application may include：
- sensor, element and function comprising different conductivity/resistivities.
- for the biocompatible materials of Bionics application.
- electronic device, including such as printed wire, logical device, component and RFID label tag for antistatic device.
- several functions coating and compound, such as ship and the nonpolluting coating or antiradar coating of marine structure
Using.
- without metal sensing apparatus and other solid-state 3D conductive equipments.
In addition, rGO or prGO films can be used to provide：For metal objects (such as steel plate and allumen (zinc
Alum)) conductive or partially electronically conductive full coat covers or part applying coating；Antimicrobial coating, such as cargo liner and cruise；Anti-corrosion
Corrosion figure layer, such as allumen fence and roof；Or antistatic film, such as counter body, storage container and electricity
Insulation.
Embodiment
It will be better understood by following preferred but non-limiting embodiment, the present invention.
Embodiment 1
The preparation of paddle graphene oxide dispersion
By improveing Hummers methods, via the reaction of graphite and potassium permanganate and concentrated sulfuric acid mixture, starting GO materials are prepared
Material.It is that the TEM and SEM of this starting GO material scheme respectively referring to Figures 5 and 6.
Then in the case of no any surfactant, by low mid power sonication 60min, by GO thin slices point
It is dispersed in pure Milli-Q water, prepares the dispersion (0.5%) of this GO material.Part evaporation Milli-Q water with vigorous stirring,
Prepare the paddle dispersion (1-2%) of GO.
Embodiment 2
The preparation of GO (graphene oxide), reGOl and reGO2 and reGO3 (' complete ' reduction GO) and feature are as follows：
Graphene oxide (GO) powder is prepared using improvement Hummer ' s methods, and by being ultrasonically treated in 50mL vials
(using butt end, 400W, 40% amplitude) 60min is scattered in pure Milli-Q water (1-5mg/mL, without any surface-active
Agent).Then dispersion is transferred directly in 60 DEG C of heating plate (Crown Scientific, Ltd.), continuously stirred strongly
It mixes, until it becomes paddle dispersion (volume is down to by 50mL close to 10mL).Then paddle dispersion is used to prepare GO films.
It is scraped using the paddle dispersion prepared by knife and/or thin GO films (brown) is coated to not by vacuum spraying method
With on matrix, the water in wet GO films is sunk into the drying in 150 DEG C of vacuum ovens immediately after with evaporation.
The matrix of the GO so prepared coatings is immersed various concentration, and (reGOl uses 0.1M ascorbic acid, and reGO2 is used
0.2M ascorbic acid and reGO3 use 0.3M ascorbic acid) ascorbic acid (reducing agent) solution in, to obtain different electronics
The reduction GO films of electrical conductivity (related from different reduced levels).Then, the graphite oxide reduced with Milli-Q water and alcohol flushing
Alkene (reGO) film (black), to remove remaining salt (because being remained during absorption), then in 120 DEG C of dryings in vacuum oven
30min。
It can also be easily using this method by changing other reducing agents of the reduction temperature application in addition to ascorbic acid.
For example, the reduction GO films with similarity can also be obtained by using NaBH4 at a lower temperature as reducing agent.
The reduction process of graphene oxide is monitored and characterized by X-ray diffraction, Raman spectrum and XPS.Fig. 3
(a)-(e) shows the correlation of these reducing conditions in Raman, XRD and XPS spectrum.
XRD and Raman spectrum properly reflect GO films to the ascorbic acid solution (0.1M-0.4M) of various concentration no
With reducing degree and ratio (see Fig. 3 (a) and (b)).For initial GO films, the main peak in XRD at 11 ° of 2 θ angles,
Corresponding to the GO main peaks of document report, with investing the high-level oxygen-containing functional group of graphene platelet both sides and in meval atom
Atomic roughness caused by the fault of construction generated on the flat graphene platelet of grade is related.Once reduction, XRD spectrums significantly change
Become.
For reGOl films, 2 θ peaks at 11 ° migrate forward 1.5 ° to 12.5 °, while 002 peak at 27 ° increases with intensity
Add sharpened, this is related with the graphene platelet of reset condition.
Further it is restored to reGO2, it can be seen that 11 ° of peaks are migrated further along to 17 °, 20-25 ° of region Zhong Jian areas
It enhances.
ReGO3 films show that main GO peaks disappear at 11 °, and two peak corresponding with reducing GO in document occurs.That is that center is located at
22 °, wide region acromialis of the intensity peak at 27.2 °.By having retained the structure of fold, remaining wide shoulder peak (from 18 ° to 25 °) table
Bright, reGO films have more unordered layered structure, this is consistent with the result of HR SEM figures.After reduction, it can be seen in XRD spectrum
Gradual change finally obtains the reGO solid films of unordered layering.
By changing the relative intensity of G and 2D bands, the variation of these increments is also be reflected in the Raman spectrum of reGO films.Fig. 3
(b) show that GO and rGO thin slices both contain three characteristic peaks positioned at 1327,1585 and 2628cm-1, be respectively D bands, G
Band and 2D bands.For GO films, 2D bands are very small and weak, and the Raman spectrum of reGO is shown, peak intensity (the inserting in Fig. 2 b of 2D bands
Figure) clearly increase with the increase of reducing degree.Further change of reduction also results in sp2:The further increase of sp3 ratios.
It is worth noting that, reGO films show apparent 2D bands, showing the average-size in sp2 domains on reGO increases.These results with
The GO heat-treated with hydrogen of document report is consistent.The increase of G ' peak intensities is further highlighted to more crystalline nature
The transformation of reGO and the reduction of oxygen-containing group.
The reduction of these significant constructive variations and oxygen-containing group is confirmed in the XPS spectrum of GO and reGO films.Fig. 3
(c)-(e) shows that the XPS of GO, reGOl and reGO3 derive the Cls regions of spectrum.For being attached on C atoms different officials
The two kinds of different components and a kind of microcomponent, the GO Cls regions of spectrum that can be rolled into a ball clearly illustrate significantly to aoxidize.This
It is the not oxygen-containing C atoms in 285eV from six side aromatic ring structures a bit, in the C-O keys of 287eV, in the carbonyl C=O of 288eV
Key, in the O=C-O bases and π-π * satellites (290.6eV) of the carboxyl combination of 289eV.
These values and document report it is very consistent.In corresponding reGOl and reGO3 collection of illustrative plates, the different reflections of collection of illustrative plates
Different amounts of electronation.In reGOl collection of illustrative plates, Cls B peaks C-O values are substantially reduced compared with C-C peaks.This intensity subtracts
Small expression ascorbic acid reduction process significantly deoxidation.As shown in reGO3 collection of illustrative plates, further reduction shows oxygen-containing group in film
The notable removal of C-O, C=O.The small peak that can be observed in document graphene collection of illustrative plates also observes that (CO (O) in this collection of illustrative plates
With C=O=O peaks).
Embodiment 3
RGO capacitors
Fig. 4 a show that the flexible interlayer type assembled with the poly- difluoroethylenes of flexible rGO/ (PVDF) prepared /rGO films is symmetrical
There are the rGO films of identical size (mass weight is each 0.456mg) in capacitor battery, both sides.RGO/PVDF/rGO films accompany
The PET thin slices (30 Ω/) of two panels tin indium oxide (ITO) coating, wherein filled with degassing aqueous electrolyte (1.0M H2SO4).
This flexible capacitor carries out entry evaluation by the constant constant current charge-discharge rate of the 0.2A shown in Fig. 4 b.Which show
Stable specific capacitance 160.2F/g and high energy density 26.1Wh/kg.
Embodiment 4
RGO compounds comprising platinum nanoparticle
New reduction scheme to prove design is suitable for GO and/or rGO compounds, and preparation is contained Pt4+GO complexes membranes
The vitreous carbon of coating is immersed in ascorbic acid, by Pt4+It is reduced to Pt0, so as to which Pt nanoparticle (PtNPs) is arranged in rGO films
On.SEM figures (after ORE tests, Fig. 4 c) and XRD spectrum disclose, and in reduction process, PtNPs is successfully loaded on reGO films.It is right
The further Primary Studies of GC its electrocatalytic oxidation reduction reaction for the PtNPs/reGO coatings being prepared, as shown in Fig. 4 (d).
The linear sweep voltammetry figure of the GC electrodes of PtNPs/reGO coatings has shown a reality in oxygen saturation 0.5M H2SO4/H2O solution
The catalytic oxidation-reduction reaction of matter, onset potential are ca.+0.61V (compared with Ag/AgCl).And under the same test conditions, in nitrogen
Reduction reaction is not observed in atmosphere.This represents that the rGO reduction scheme of exploitation can be used to prepare reGO nano-complexes, useful
In by application extension to energy conversion and association area potential.
Embodiment 5
RGO films biology catalytic activity is studied
It is believed that the biology catalytic activity of graphite carbon electrode is essentially from functional group's defect sites.Therefore, study portion
ReGO films (on PET thin slices/glass of ITO coatings, Fig. 4 e) are reduced, by differential pulse voltammetry (DPV) in PBS buffer solution
(pH=7.0) detection dopamine (DA) in.DPV curves in Fig. 4 f show clear DA oxidation peaks, with the increase of DA concentration
(from 5 μ Μ to 100 μ Μ) and increase.This represents that the reGO films of partial reduction are expected to as electrode material, by controlling reGO
The reduced level of film detects for DA, can not only control/maintain specific degree of functionality for living things catalysis performance, and
Rational electrical conductivity can be obtained for electric charge transfer.
Claims (15)
1. a kind of method for the graphene oxide for producing reduction or partial reduction, the method comprising the steps of：
(a) matrix that surface includes graphene oxide layer is provided；And
(b) selectively reducing agent solution is printed onto in graphene oxide layer so that the selection area in graphene oxide layer
The middle graphene oxide layer for forming reduction or partial reduction.
It 2. selectively will more reducing agent solution printings according to the method described in claim 1, further including step (c)
Onto at least part selection area.
3. according to the method described in claim 2, wherein step (c) is repeated one or more times.
4. according to the method described in claim 1, wherein step (a) includes graphene oxide dispersion being coated or deposited on base
On body surface face.
5. according to the method described in claim 4, wherein the dispersion of graphene oxide includes point of graphene oxide in water
Granular media.
6. according to the method described in claim 1, wherein reducing agent is printed using inkjet printing.
7. method according to claim 1 or 2, wherein reducing agent solution are aqueous solution.
8. according to the method described in claim 7, the reducing agent wherein in reducing agent solution is ascorbic acid.
9. according to the method described in claim 1, wherein reduction or partial reduction graphene oxide electrical conductivity be more than
1000S/cm。
10. according to the method described in claim 1, a graphene oxide compound is included wherein on the matrix surface of step (a)
Material layer.
11. a kind of matrix, surface includes the graphene oxide of the reduction or partial reduction according to the production of claim 1 or 2.
12. a kind of matrix according to claim 11, wherein the form of the graphene oxide layer of reduction or partial reduction is
Circuit pattern.
13. a kind of matrix according to claim 11 or 12, wherein the thickness of reduction or partial reduction graphene oxide layer
Less than 2 μm.
14. the reduction produced according to the method described in claim 1 or 2 or the graphene oxide of partial reduction are as conductive or portion
Divide the purposes of conductive coating, antimicrobial coating, corrosion-inhibiting coating or antistatic coating.
15. the reduction or the graphene oxide of partial reduction that are produced on according to the matrix described in claim 11 are used as conductor
In the purposes of the electrical conduction of electric power.
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| AU2011903840 | 2011-09-19 | ||
| AU2011903840A AU2011903840A0 (en) | 2011-09-19 | Reduced graphene oxide and method of producing same | |
| PCT/AU2012/001124 WO2013040636A1 (en) | 2011-09-19 | 2012-09-19 | Reduced graphene oxide and method of producing same |
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