CN104039695A - Reduced graphene oxide and method of producing same - Google Patents
Reduced graphene oxide and method of producing same Download PDFInfo
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- CN104039695A CN104039695A CN201280056867.8A CN201280056867A CN104039695A CN 104039695 A CN104039695 A CN 104039695A CN 201280056867 A CN201280056867 A CN 201280056867A CN 104039695 A CN104039695 A CN 104039695A
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Abstract
There is provided a method of producing reduced (rGO) or partially reduced (prGO) Graphene Oxide films that have improved conductivity. The method is capable of creating highly conducting (-2000 S/cm), flexible, printable, processable reduced graphene oxide materials without the need for harsh chemical treatment or high temperature annealing. In one embodiment, an electrical circuit consisting of reduced graphene oxide tracks may be patterned into a graphene oxide film by printing with a reducing agent, preferably ascorbic acid.
Description
Technical field
The present invention relates to a kind of method of the graphene oxide of producing reduction and/or partial reduction.
Background technology
Grapheme material provides the highest known conductivity for single-layer system.Therefore, expection Graphene and class grapheme material will become the main raw of electronics of future generation.
Graphene is generally produced by mechanically peel method or chemical vapour deposition (CVD) method.Although these methods can both be produced high-crystallinity high conductivity Graphene, for scale operation, they conventionally can not mass-producing or not cost-effective.
Another kind method is chemical reduction graphene oxide (GO), and it is easily produced by graphite.But, although can relatively easily produce graphene oxide material, but follow-uply can only obtain so far poor specific conductivity (~10-100S/cm) to the reducing process of class grapheme material, differ greatly with the specific conductivity (>3000S/cm) of pure Graphene.Product through reduction is commonly referred to as redox graphene (rGO or reGO).The redox graphene (rGO) and the partial reduction graphene oxide (prGO) that utilize existing method to produce are similar to Graphene aspect crystalline network, but have the defect of residual oxygen and structure aspects.With respect to Graphene, these defects have significantly reduced the specific conductivity of report.But those of specific conductivity and conductive doped polymkeric substance and silicon are suitable.
Aftertreatment or high temperature annealing can make specific conductivity up to 500-700S/cm, but such treatment condition are infeasible in semi-conductor industry, and do not have 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 material produce rGO.For example, by GO thin slice is immersed in hydrazine, the combinations produce that is exposed to hydrazine steam, electrochemical reduction, thermal annealing and these technology goes out the Graphene that chemical process obtains.The most frequently used chemistry route is by using hydrazine, toxicity reductive agent, and follow-up high temperature annealing.But the rGO film of being produced by these methods is limited aspect exploitation, and the rGO specific conductivity up to the present obtaining is low, internal resistance is high.
Another kind method is, by the resistive heating of AFM cantilever, GO is carried out to adjustable reduction.But, this method is not suitable for large-scale commercial applications production technology.
Graphene oxide (GO) sill is potential for far-ranging application, comprises that storing device, sensing platform, cell cultures, electrochemical energy source device, high sensitive gas sensor and quality factor exceed the mechanical resonator of Graphene resonator.The room temperature band gap of GO is greater than 0.5eV, has localization semi-conductor and semi-metal characteristic simultaneously, and this is because it is reduced towards class grapheme material direction.
The present invention attempts providing in one simply can chemical process mass-producing and ecological sustainability; with production high conductivity (~2000S/cm), flexibility, can print, machinable redox graphene material, and do not need harsh chemical treatment or high temperature annealing.
Summary of the invention
In a kind of more wide in range form of the present invention (form), a kind of method of the graphene oxide of producing reduction or partial reduction is provided, the method comprising the steps of:
(a) provide graphene oxide; With
(b) reductive agent is added at least part of graphene oxide.
In further form, step (a) comprises provides matrix, and described matrix surface comprises graphene oxide.
In further form, the matrix surface of step (a) comprises graphene oxide layer.
In further form, generate from the teeth outwards the graphene oxide layer of reduction or partial reduction.
In further form, reductive agent is optionally applied on graphene oxide layer, makes the graphene oxide of reduction or partial reduction in graphene oxide layer, form a pattern (pattern).
In further form, step (a) comprises the coating of graphene oxide dispersion or is deposited on the surface of matrix.
In one form, the dispersion of graphene oxide comprises the dispersion of graphene oxide in water.
In another form, the reductive agent of step (b) applies as a part for solution.
In further form, step (b) comprise the matrix surface that comprises graphene oxide is immersed or dip-coating in the solution that comprises reductive agent.
In one form, step (b) comprises the solution that comprises reductive agent is printed onto on the matrix that comprises graphene oxide.
In one form, printing comprises intaglio printing, volume to volume (roll-to-roll) printing, reel-to-reel (reel-to-reel) printing, spray ink Printing or flexographic printing.
In further form, the solution that comprises reductive agent is the aqueous solution.
In one form, the reductive agent applying is xitix.
In another form, the specific conductivity of the graphene oxide of reduction or partial reduction is about between 0-5000S/cm.
In further form, on the matrix surface of step (a), comprise graphene oxide composite materials layer.
In further form, the invention provides according to the matrix of graphene oxide that comprises reduction or partial reduction on the surface of any production in above-mentioned form.
In one form, the form of the graphene oxide of reduction or partial reduction is circuit pattern (circuit pattern).
In one form, the invention provides according to the equipment (device) of the graphene oxide that comprises reduction or partial reduction of any production in above-mentioned form.
In one form, the invention provides the matrix of the graphene oxide layer in its surface with reduction or partial reduction, the thickness of this layer is less than 2 μ m, and specific conductivity is greater than 1000S/cm.
In one form, the invention provides the graphene oxide of the reduction of producing according to any method in above-mentioned form or partial reduction as the purposes of conduction or partially conductive coating, antimicrobial coating, corrosion protection coating or antistatic coating.
In one form, the graphene oxide that the invention provides the reduction of producing according to any method in above-mentioned form or partial reduction is the purposes for the conductivity of electric power as conductor.
Brief description of the drawings
Below with reference to accompanying drawing, the various non-limiting embodiments of the present invention are described in detail, the present invention will become and be easier to understand, wherein:
Fig. 1 has shown the rGO trace (track) that uses conventional ink jet printers to produce in GO film;
Fig. 2 has shown the rGO layer of different thickness;
Fig. 3 a is natural GO, reGOl, 2 and 3 X ray diffracting spectrum;
Fig. 3 b is the Raman spectrum obtaining at 633nm, has shown D, G, 2D and the G ' region (the more detailed view of 2D and G ' region in illustration-spectrum) of spectrum;
Fig. 3 c is the x-ray photoelectron power spectrum in the C1 region of GO;
Fig. 3 d is the x-ray photoelectron power spectrum in the C1 region of reGO1;
Fig. 3 e is the x-ray photoelectron power spectrum in the C1 region of reGO3;
Fig. 4 a has shown the symmetrical capacitor battery of flexible sandwich-like of flexible rGO/ poly-difluoroethylene (the PVDF)/rGO film assembling that utilizes preparation, and there is the rGO film of same size (quality weight is each 0.456mg) its both sides;
Fig. 4 b has shown the continuous current charge-discharge rate of the electrical condenser in Fig. 4 a;
Fig. 4 c is the SEM image of the rGO film that comprises Pt nanoparticle;
Fig. 4 d is the linear sweep voltammetry figure of the rGO film that comprises Pt nanoparticle;
Fig. 4 e has shown PET sheet/partial reduction rGO film on glass that ITO applies;
Fig. 4 f is the differential pulse voltammetry DPV that partial reduction GO surface is carried out, to detect the Dopamine HCL of deposition;
Fig. 5 is the transmission electronic MIcrosope image of GO before reduction;
Fig. 6 is the scanning electron microscope image of GO before reduction;
Fig. 7 a has shown the rGO circuit that lifts the ink-jet impression on GO on front slide glass;
Fig. 7 b has shown and having lifted the rGO circuit of Fig. 7 a independently after the band that removes photoresist;
Fig. 8 has shown and the adhesive tape of GO/RGO has been lifted to formed independent circuits and the example of equipment from slide glass;
Fig. 9 a shown lift before with adhesive tape by spray ink Printing in patterned RGO dipole RFID label design on glass;
Fig. 9 b has shown and is lifting the RFID label as Fig. 9 a of independent means after the band that removes photoresist;
Figure 10 a has shown the GO that covers the RGO pattern of changing with 10x10mm on ito glass;
Figure 10 b has shown that adhesive tape starts the RGO of Figure 10 a staying after GO;
Figure 11 a has shown the ink-jet impression RGO circuit in the GO on ito glass matrix; And
Figure 11 b has shown the ink-jet impression RGO that removes Figure 11 a after GO with adhesive tape, and the LED of its surface mounting is attached with silver paint.
Embodiment
Description is above only embodiments more of the present invention, in the situation that not deviating from scope and spirit of the present invention, can modify and/or change, and these embodiments are illustrative, and nonrestrictive.
In the context of the present specification, word " comprises " and refers to " substantially contain but needn't uniquely contain " or " having " or " containing ", but not " only by ... form ".The distortion that word " comprises (comprising) ", for example, " comprise (comprise) " and " comprising (comprises) " has a corresponding various meaning.
Some embodiment provides the method for a kind of production reduction (rGO) or partial reduction (prGO) graphene oxide film, and described film has the specific conductivity of raising than the rGO film of preparing by other method.
In addition, the inventive method can environment for use friendly and easy process choice redox graphene (GO) film of mass-producing.
The method that the present invention describes will be deposited on GO on matrix reduction, instead of GO in chemical reducing solution and subsequently rGO is coated to surface.Contriver has shown that the new purposes of improvement to processing sequence and specific reductant is to show remarkable advantage.Advantageously, in the methods of the invention, GO film can be used reductive agent impression or printing, to produce the rGO trace of highly conductive in GO dielectric substrate.
The advantage of method described herein comprises:
The specific conductivity (~3000S/cm) of the Graphene that-specific conductivity that records generates close to pure CVD
-do not need high temperature or finishing sequence.Conventionally, present method can be implemented at ambient temperature.This is an important factor in for example electron trade, because back-end chip technical requirements program temperature is lower than 300 DEG C.
-can environment for use friendly with operation reductive agent, for example xitix.
In certain embodiments, prepare graphene oxide when beginning and deposit the matrix on it.The matrix with graphene oxide can be prepared with different modes.In general, first prepare the slurry formula dispersion of GO.GO dispersion can comprise the dispersion of GO in water, ethanol, ionic liquid, solvent or other liquid vehicle.Liquid vehicle can comprise glycol ether, for example, and diethylene glycol monobutyl ether, Diethylene Glycol n-butyl ether acetic ester, ethylene glycol n-butyl ether acetate or ethylene glycol monobutyl ether.
Wt% graphene oxide in graphene oxide dispersion is variable, and generally through selecting the final application of the rGO material to be applicable to GO or produce subsequently.For example, graphene oxide dispersion can comprise low (being less than 0.5wt%), in the graphene oxide of (between 0.5wt% to 2.0wt%) and high (being greater than 2wt%) concentration.
GO dispersion can further comprise following any or combination: biological reagent, enzyme, cell, polymkeric substance, fiber, ionic liquid, nano material (for example nano particle, nanotube, nanometer sheet and nanometer rod) and/or other active precursor (for example monomer, AgNO
3, AuCl
3and H
2ptCl
6, and other metal-salt).
Once prepare, can then slurry formula GO dispersion be deposited on the surface of matrix.Can deposit GO by apply widely/deposition technique of use range, comprise that cutter is coated with, sprays (such as air spraying), spray ink Printing, silk screen printing, spin coating, drips casting, dip-coating, brushing, intaglio printing, flexographic printing, blade coating, gauge stick coating, channel mould coating etc.Filtration, Langmuir-Blodgett, electrospinning or fiber sprinning.
It will be appreciated by those skilled in the art that base material can be rigidity, flexibility or soft.For example, matrix can comprise film, by metal, polymkeric substance, film, glass, silicon, other coating and or even crystal multilayer or the 3D structure made.For example, matrix can be matrix, rubber, polymer gel, hydrogel, SPE film, crosslinked SPE, fabric (as cloth), the senior fabric (as Kevlar or Gortex) of slide glass, solid metal sheet, metal or metal matrix paper tinsel (as Copper Foil or aluminium foil), plastic sheet (for example PET or Au-Mylar), film (for example PVDF), paper, polymer-based carbon, or fiber of future generation (as graphene oxide fiber).
It will be appreciated by those skilled in the art that matrix surface can comprise GO composite materials.
In addition, a part for the compound GO material of act or omission, matrix surface can comprise biological reagent, enzyme, cell, polymkeric substance, fiber, ionic liquid, nano material, nano particle, nanotube, nanometer sheet, nanometer rod, active precursor, monomer, AgNO
3, AuCl
3and H
2ptCl
6and any or combination in other metal-salt.
For obtaining rGO or prGO, as required, reductive agent is added in the GO on matrix.Reductive agent is generally a part for solution.The solution that comprises reductive agent can be the aqueous solution, organic solution or ionic liquid.Solution can comprise glycol ether, for example, and diethylene glycol monobutyl ether, Diethylene Glycol n-butyl ether acetic ester, ethylene glycol n-butyl ether acetate or ethylene glycol monobutyl ether.
Reductive agent can be inorganic or organic.For example, reductive agent can comprise xitix, oxalic acid (C
2h
2o
4), formic acid (HCOOH), sodium borohydride (NaBH
4), cell, lithium aluminium hydride (LiAlH
4), sulfite compound, phosphite, phosphorous acid or citric acid.Reductive agent can be also electroactive polymer.
Xitix is naturally occurring compound, and can be used as the aqueous solution and provide, thereby an eco-friendly reductive agent is provided.
GO reduced level and the synthetic rGO specific conductivity that obtains thus can be exposed to by changing type, temperature and the GO of concentration, reductive agent of reductive agent the time of reductive agent and control.Optionally apply reductive agent so that conduction rGO pattern to be provided in insulation GO matrix.
Can apply reductive agent by the various technology that include but not limited to dip-coating or printing.Printing comprises intaglio printing, volume to volume printing, reel-to-reel printing, spray ink Printing or flexographic printing.Also can use gas phase impression (vapour phase patterning) to apply reductive agent.
Fig. 1 has shown the selection area reduction that uses the conventional ink jet printers that is loaded with reductive agent to carry out GO film.In this embodiment, characteristic dimension is subject to the restriction of inkjet nozzle, but this method can a step be printed a series of components.The ball bearing made using that Fig. 1 shows has shown rGO trace, and surface resistivity is 200 Ω/, becomes the pattern in GO film by spray ink Printing.In the time using spray ink Printing, by regulating drop size and the time of drying of reductive agent, can further regulate the specific conductivity of the rGO trace producing in GO film.
The rectangular patterns that Fig. 2 shows has shown the different resistivity structure of producing according to the inventive method.By changing the number of layer of reductive agent type channel or coating, can obtain different resistivity.From the left side, rectangle represents respectively the resistivity of 120 Κ Ω (1 passage), 13 Κ Ω (2 passage), 2 Κ Ω (5 passage), 600 Ω (10 passage), 200 Ω/sq (15 passage).
The thickness of reduction or partial reduction graphene oxide layer can be different according to required application.
For the application of 3D equipment, can on matrix, deposit the coat of a series of GO " paper ", then apply reductive agent.Along with the deposition of every one deck, also can apply structural fix/bonding agent to the GO not reducing.This can produce the 3D rGO equipment of high conduction in the GO of high-insulation matrix.These matrix can be potentially by mechanical workout to produce, for example for the sensing apparatus in Stability Analysis of Structures insulated platform (for example, the loud speaker of all size ranges, from earphone to large size loud speaker, electromagnet, engine, transformer etc.) without metal solid air core coil or metal-cored coil and spiral tube.Or rGO " paper " itself can layer by layer deposition, or for this process, can use previously prepared " paper " of customized thickness.
In addition, develop a selectivity of easily going and lifted except technique (lift-off process), figuratum seal rGO feature has been removed from matrix, to form independently rGO structure and equipment of flexibility.This technique generally needs an adhesive tape, and its adhesive side is to being placed down on the GO/rGO surface of generation.Then adhesive tape is started from support substrate carefully.In lifting except process, the surface energy of matrix determines the degree that rGO removes.Also can optionally remove unconverted GO region, rGO pattern is stayed to matrix surface.
Relatively hydrophilic and rGO is more hydrophobic through the GO applying.Therefore, the pattern transforming as rGO is on hydrophobic surface time, and bounding force is enough to resist adhesive tape and lifts and remove.At more not hydrophobic matrix, as on glass, rGO will be removed with together with GO region around.In this case, can use second adhesive tape so that the adhesive tape starting is carried out to lamination, protection rGO pattern also forms independently pattern of flexibility.
Lift divided by the embodiment that produces independent means and be presented in Fig. 7-9 from slide glass.The unconverted GO material of selective removal on glass applying from more hydrophobic ITO is presented at Figure 10 and 11.
For the embodiment of Figure 11, the glass that generates the ITO coating of rGO pattern on it is scraped to form off two discrete contact blocks.LED is attached on the rGO of every discrete contact block.Realize with contacting by the rGO contact pad from ITO conductive electrode below of LED.
Be also to be understood that reductive agent also can give other character of rGO layer of generation.The reductive agent component with the rear compound rGO material of reduction as reductive agent simultaneously.
For example, can use acid electroactive conductive polymers as reductive agent.It is acid that this polymkeric substance is, reduction GO.Except reduction, polymkeric substance also for rGO provide electroactive character (for example, can conduction and state of insulation between reversible transformation).
The RFID label of Fig. 9 is by the electroactive conductive polymers preparation of stamping ink dissolubility.
The method that therefore the inventive method can provide 1 step to manufacture rGO/ equipment complex by printing function reductive agent, and need not first form rGO pattern, then chromatography functional material carrys out finishing equipment.
In addition, this 1 one step process can form the 3D network of bi-material, and multistep method forms polymeric film on the surface of rGO pattern.
As described, contriver shown the high conduction of preparation (~2000S/cm) redox graphene structure adjustable, can expand, the chemical process of continuity of environment, and do not need harsh chemical processing or annealing.
The present invention can also produce in a kind of extendible mode the pattern of different resistivity in preformed graphene oxide structure.By changing parameter for example reductant concentration, reductive agent or temperature, those skilled in the art can control the resistivity of the rGO acquisition of generation.The inventive method can obtain the sheet resistivity that is low to moderate 2Ohm/sq.Such resistivity is equivalent to the resistivity of the Graphene that approaches CVD generation.In addition, the reductive agent applying in method can pass through spray ink Printing, makes to produce electric circuit construction by a step program.
These structural tables understand the unprecedented control to redox graphene character, thereby have obtained class Graphene specific conductivity.This control can realize almost unlimited process choice, and described selection is applicable to a series of typography, and for example ink-jet, volume to volume and reel are to reel technology.
Method described herein provides the chance of producing a collection of redox graphene application of future generation and equipment.For example, method of the present invention can be used for producing electrode, sensor, bionical equipment, energy conversion, fuel cell, solar cell, water decomposition battery, water and cleans battery, energy storage devices, rechargeable cell, ultracapacitor, hybrid battery, electronics, display equipment, electrochromism battery, interchange/assets tracing equipment, passive or active RFID tag, electrochemical apparatus and/or can wearable device.
Other application can comprise:
-sensor, the element that comprises different conductivity/resistivity and function.
-for the biocompatible materials of Bionics application.
-electron device, comprises printed wiring for example, logical device, assembly and RFID label for antistatic device.
-several functions coating and mixture, for example, apply for antifouling coating or the destructive interference coating of ship and marine structure.
-without metal sensing apparatus and other solid-state 3D conductive equipment.
In addition, rGO or prGO film can be in order to provide: for example, for metal objects (steel plate and aluminium zinc (zinc alum)) conduction or partially conductive full coat covers or part applying coating; Antimicrobial coating, for example, for cargo liner and cruise; Anticorrosion corrosion figure layer, for example, for aluminium zinc fence and roof; Or antistatic film, for example, for counter body, storage receptacle and electrical isolation.
Embodiment
By following preferred but nonrestrictive embodiment, the present invention will be better understood.
Embodiment 1
The preparation of slurry formula graphene oxide dispersion
By improvement Hummers method, via reacting of graphite and potassium permanganate and vitriol oil mixture, prepare initial GO material.Referring to Fig. 5 and 6, be respectively TEM and the SEM figure of this initial GO material.
Then without any tensio-active agent in the situation that, by low mid power sonication 60min, GO thin slice is dispersed in pure Milli-Q water, prepares the dispersion (0.5%) of this GO material.Under vigorous stirring, part is evaporated Milli-Q water, the slurry formula dispersion (1-2%) of preparation GO.
Embodiment 2
Preparation and the feature of GO (graphene oxide), reGOl and reGO2 and reGO3 (' complete ' reduction GO) are as follows:
Graphene oxide (GO) powder uses improvement Hummer ' s legal system standby, and (use butt end by supersound process in 50mL vial, 400W, 40% amplitude) 60min is scattered in (1-5mg/mL, without any tensio-active agent) in pure Milli-Q water.Then the hot-plate (Crown Scientific, Ltd.) of dispersion directly being transferred to 60 DEG C is upper, and violent stirring continuously, until it becomes slurry formula dispersion (volume is down to and is approached 10mL by 50mL).Then will starch formula dispersion for the preparation of GO film.
The slurry formula dispersion that use prepares is scraped by cutter and/or vacuum spraying method is coated to thin GO film (brown) in different matrix, then dry in 150 DEG C of vacuum ovens immediately, to evaporate the water sinking in wet GO film.
The matrix that the GO of so preparation is applied immerses different concns, and (reGOl uses 0.1M xitix, reGO2 uses 0.2M xitix and reGO3 to use 0.3M xitix) xitix (reductive agent) solution in, to obtain the reduction GO film of different electronic conductivities (relevant from different reduced levels).Then, with graphene oxide (reGO) film (black) of Milli-Q water and alcohol flushing reduction, with remove residual salt (because of absorption residual), then in vacuum oven in 120 DEG C of dry 30min.
Can also easily use the method to apply other reductive agent except xitix by changing reduction temperature.For example, use at a lower temperature NaBH4 also can obtain the reduction GO film with similarity as reductive agent.
By X-ray diffraction, Raman spectrum and XPS, the reduction process of graphene oxide is monitored and characterized.Fig. 3 (a)-(e) shown dependency of these reduced states in Raman, XRD and XPS spectrum.
XRD and Raman spectrum have reflected the different reducing degrees of the ascorbic acid solution (0.1M-0.4M) of GO film to different concns and ratio (see Fig. 3 (a) and (b)) rightly.For initial GO film, main peak in XRD appears at the 2 θ angle places of 11 °, corresponding to the GO main peak of bibliographical information, its atomic roughness causing with the textural defect that invests the high-level oxygen-containing functional group of graphene platelet both sides and produce on the flat graphene platelet of meval atom level is relevant.Once reduction, XRD spectrum significantly changes.
For reGOl film, 11 ° of 2 θ peaks of locating move forward 1.5 ° to 12.5 °, and 27 ° of 002 peaks of locating are along with strength increase is sharpened simultaneously, and this is relevant with the graphene platelet of virgin state.
Further be reduced to reGO2, can see that 11 ° of peaks further migrate to forward 17 °, Zhong Jian district, 20-25 ° of region has strengthened.
ReGO3 film show 11 ° locate main GO peak disappear, with in document, reduce GO corresponding two peaks occur.That is to be centered close to 22 °, intensity peak at the wide region acromialis of 27.2 °.Play the structure of fold by reservation, all the other wide shoulder formula peaks (from 18 ° to 25 °) show, reGO film has more unordered layered structure, and this is consistent with the result of HR SEM figure.After reduction, in XRD figure spectrum, can see gradual change, finally obtain the reGO solid film of unordered layering.
By changing the relative intensity of G and 2D band, these increments variations are also reflected in the Raman spectrum of reGO film.Fig. 3 (b) has shown that GO and rGO thin slice all contain and has been positioned at 1327,1585 and three characteristic peaks of 2628cm-1, has been respectively D band, G band and 2D band.For GO film, 2D band is very small and weak, and the Raman spectrum of reGO shows, the peak intensity (illustration in Fig. 2 b) of 2D band clearly increases with the increase of reducing degree.The further change of reduction also causes the further increase of sp2:sp3 ratio.It should be noted that reGO film presents obvious 2D band, show that the mean sizes in the upper sp2 of reGO territory increases.These results and bibliographical information to carry out the GO of thermal reduction with hydrogen consistent.The increase of G ' peak intensity has further been given prominence to the transformation of reGO and the reduction of oxy radical that have more crystalline nature.
The reduction of these significant constructive variations and oxy radical is confirmed in the XPS spectrum of GO and reGO film.Fig. 3 (c)-(e) shown that the XPS of GO, reGOl and reGO3 derives the Cls region of spectrum.For two kinds of different components and a kind of minor component that can be connected to different functional groups on C atom, the GO Cls region of spectrum clearly illustrates that significantly oxidation.These are the oxygen-free C atoms in 285eV from hexagon aromatic ring structure, at the C-O of 287eV key, and at the carbonyl C=O of 288eV key, at the O=C-O base of the carboxyl combination of 289eV, and π-π * satellites (290.6eV).
These values are very consistent with bibliographical information.In corresponding reGOl and reGO3 collection of illustrative plates, the difference of collection of illustrative plates has reflected the chemical reduction of different amounts.In reGOl collection of illustrative plates, Cls B peak C-O value significantly reduces with respect to C-C peak.This intensity reduce to represent the significantly deoxidation of xitix reduction process.As shown in reGO3 collection of illustrative plates, further reduction has shown the remarkable removal of oxy radical C-O, C=O in film.The small peak that can observe in document Graphene collection of illustrative plates also can be observed (CO (O) and C=O=O peak) in this collection of illustrative plates.
Embodiment 3
RGO electrical condenser
Fig. 4 a has shown that there is the rGO film of same size (quality weight is each 0.456mg) its both sides with the symmetrical capacitor battery of flexible sandwich-like of flexible rGO/ poly-difluoroethylene (PVDF)/rGO film assembling of preparation.RGO/PVDF/rGO film accompanies the PET thin slice (30 Ω/) that two tin indium oxides (ITO) apply, and is wherein filled with degassed aqueous electrolyte (1.0M H2SO4).This flexible capacitor is carried out entry evaluation by the constant constant current charge-discharge rate of the 0.2A that shows in Fig. 4 b.It has provided stable than electric capacity 160.2F/g and high energy density 26.1Wh/kg.
Embodiment 4
The rGO mixture that comprises platinum nanoparticle
For the new reduction scheme that proves design is applicable to GO and/or rGO mixture, by the Pt that contains of preparation
4+the vitreous carbon that GO complexes membrane applies immerses in xitix, by Pt
4+be reduced to Pt
0thereby, Pt nanoparticle (PtNPs) is arranged on rGO film.(after ORE test, Fig. 4 c) discloses with XRD figure spectrum SEM figure, and in reduction process, PtNPs successfully loads on reGO film.Its electrocatalytic oxidation reduction reaction of the further preliminary study of GC that the PtNPs/reGO of such preparation is applied, as shown in Fig. 4 (d).The linear sweep voltammetry chart of the GC electrode that PtNPs/reGO applies understands the catalytic oxidation-reduction reaction of an essence in oxygen saturation 0.5M H2SO4/H2O solution, and onset potential is ca.+0.61V (with respect to Ag/AgCl).And under same test condition, in nitrogen atmosphere, do not observe reduction reaction.This rGO reduction scheme that represents exploitation can be in order to prepare reGO nano-complex, is useful on the potential to Conversion of energy and association area by application extension.
Embodiment 5
The research of rGO film biology catalytic activity
It is believed that, the biology catalytic activity of graphite carbon electrode is mainly from functional group's defect sites.Therefore, (the PET thin slice that applies at ITO/on glass, Fig. 4 e), detects Dopamine HCL (DA) to study portion reduction reGO film in PBS damping fluid (pH=7.0) by differential pulse voltammetry (DPV).DPV curve display in Fig. 4 f DA oxidation peak clearly, increase with the increase (from 5 μ Μ to 100 μ Μ) of DA concentration.This reGO film that represents partial reduction is expected to as electrode materials, detect for DA by the reduced level of controlling reGO film, can not only control/maintain specific degree of functionality for biocatalysis performance, and can obtain rational specific conductivity and shift for electric charge.
Claims (21)
1. a method of producing the graphene oxide of reduction or partial reduction, the method comprising the steps of:
(a) provide graphene oxide; And
(b) reductive agent is added at least part of graphene oxide.
2. method according to claim 1, wherein the matrix that provides a surface to comprise graphene oxide is provided step (a).
3. method according to claim 2, wherein comprises a graphene oxide layer on the matrix surface of step (a).
4. method according to claim 3, wherein the graphene oxide layer of generation reduction or partial reduction on described surface.
5. method according to claim 4, wherein reductive agent is optionally applied on graphene oxide layer, makes the graphene oxide of reduction or partial reduction in graphene oxide layer, form a pattern.
6. according to the method described in claim 2-5 any one, wherein step (a) comprises the coating of graphene oxide dispersion or is deposited on matrix surface.
7. method according to claim 6, wherein the dispersion of graphene oxide comprises the dispersion of graphene oxide in water.
8. according to the method described in claim 2-7 any one, wherein the reductive agent of step (b) applies as a part for solution.
9. method according to claim 8, wherein step (b) comprise the matrix surface that comprises graphene oxide is immersed or dip-coating in the solution that comprises reductive agent.
10. method according to claim 8, wherein step (b) comprises the solution that comprises reductive agent is printed onto on the matrix that comprises graphene oxide.
11. methods according to claim 10, wherein printing comprises intaglio printing, volume to volume printing, reel-to-reel printing, spray ink Printing or flexographic printing.
Method described in 12. according to Claim 8-11 any one, the solution that wherein comprises reductive agent is the aqueous solution.
13. according to the method described in claim any one above, and the reductive agent wherein applying is xitix.
14. according to the method described in claim any one above, and wherein the specific conductivity of the graphene oxide of reduction or partial reduction is about between 0-5000S/cm.
15. according to the method described in claim 2-14 any one, wherein on the matrix surface of step (a), comprises a graphene oxide composite materials layer.
16. 1 kinds of matrixes, its surface comprises according to the reduction of claim any one production above or the graphene oxide of partial reduction.
17. matrixes according to claim 16, wherein the form of the graphene oxide of reduction or partial reduction is circuit pattern.
18. 1 kinds of equipment, it comprises according to the reduction of claim 1-15 any one production or the graphene oxide of partial reduction.
19. 1 kinds of matrixes, its surface has the graphene oxide layer of reduction or partial reduction, and the thickness of this layer is less than 2 μ m, and specific conductivity is greater than 1000S/cm.
The graphene oxide of 20. reduction of producing according to the method described in claim 1-15 any one or partial reduction is as the purposes of conduction or partially conductive coating, antimicrobial coating, corrosion protection coating or antistatic coating.
The graphene oxide of 21. reduction of producing according to the method described in claim 1-15 any one or partial reduction is the purposes for the conductivity of electric power as conductor.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090146111A1 (en) * | 2007-12-07 | 2009-06-11 | Samsung Electronics Co., Ltd. | Reduced graphene oxide doped with dopant, thin layer and transparent electrode |
US20090235721A1 (en) * | 2008-03-20 | 2009-09-24 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Reduced graphene oxide film |
US20110143101A1 (en) * | 2009-12-11 | 2011-06-16 | Adarsh Sandhu | Graphene structure, method for producing the same, electronic device element and electronic device |
US20110180140A1 (en) * | 2010-01-28 | 2011-07-28 | University Of Central Florida Research Foundation, Inc. | Supramolecular structures comprising at least partially conjugated polymers attached to carbon nanotubes or graphenes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100000441A1 (en) * | 2008-07-01 | 2010-01-07 | Jang Bor Z | Nano graphene platelet-based conductive inks |
-
2012
- 2012-09-19 CN CN201280056867.8A patent/CN104039695B/en not_active Expired - Fee Related
- 2012-09-19 KR KR1020147010324A patent/KR20140093930A/en not_active Application Discontinuation
- 2012-09-19 WO PCT/AU2012/001124 patent/WO2013040636A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090146111A1 (en) * | 2007-12-07 | 2009-06-11 | Samsung Electronics Co., Ltd. | Reduced graphene oxide doped with dopant, thin layer and transparent electrode |
US20090235721A1 (en) * | 2008-03-20 | 2009-09-24 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Reduced graphene oxide film |
US20110143101A1 (en) * | 2009-12-11 | 2011-06-16 | Adarsh Sandhu | Graphene structure, method for producing the same, electronic device element and electronic device |
US20110180140A1 (en) * | 2010-01-28 | 2011-07-28 | University Of Central Florida Research Foundation, Inc. | Supramolecular structures comprising at least partially conjugated polymers attached to carbon nanotubes or graphenes |
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