CN105084348B - A kind of method for preparing the mutually dispersible conductive graphene dispersion slurries of water or solid - Google Patents
A kind of method for preparing the mutually dispersible conductive graphene dispersion slurries of water or solid Download PDFInfo
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Abstract
The present invention is a kind of method for preparing the mutually dispersible conductive graphene dispersion slurries of water or solid.The water-soluble graphene slurries and solid material are prepared using non-covalent approach, are comprised the following steps：By it is a certain amount of to add shake in deionized water with certain water miscible ionic liquid shake up, then ultrasound or concussion dispersion in the aqueous solution of the above-mentioned ionic liquid of a certain amount of high conductivity Graphene addition are weighed, is obtained through ion liquid modified water phase dispersibility conductive graphene dispersion slurries.By above-mentioned slurries, by vacuum freeze drying or under conditions of less than 100 degrees Celsius, drying goes moisture removal to obtain the Graphene solid with water phase dispersibility.The grapheme material of the ion liquid functionalization obtained by the present invention has preferably dispersiveness and dissolubility in hydrophilic solvent.Preparation method of the present invention and the conductive graphene with aqueous phase dispersibility for preparing can be widely used in the fields such as chemical sensitisation, bio-sensing, energy storage, device, catalysis, analysis.
Description
Technical field
Prepared the invention belongs to material and bio-sensing field, be related to conductive graphene slurries with aqueous phase dispersibility and
Application of the preparation method and its associated materials and method of solid in fields such as sensor, energy storage.
Background technology
Graphene (Graphene, abridge GR) is that one kind constitutes hexangle type in honeycomb crystalline substance by carbon atom with sp2 hybridized orbits
The flat film of lattice, the two-dimensional material of only one of which carbon atom thickness.It is but also most hard that Graphene is currently world most thin
Nano material；Thermal conductivity factor is up to 5300W/mK, higher than CNT and diamond, its resistivity about 10 under normal temperature-6
Ω cm, it is lower than copper or silver, it is the minimum material of world resistivity.Because Graphene is substantially a kind of transparent, good
Conductor, it is in device (electronic component or transistor), energy storage (solar cell, lithium battery, ultracapacitor), catalysis, chemistry
The aspect such as sensing and bio-sensing has wide application prospect.
Graphenic surface is hydrophobic, and it is considered as always impossibility that Graphene is directly dispersing in aqueous phase system
Feelings.Graphene has very big specific surface area, and hydrophobic surface is reunited with arriving easily in water phase and settled together.With carbon tubing
Seemingly, it is the crucial step that material moves towards application to solve its dispersiveness.The intrinsic hydrophobic nature of Graphene gives it in many fields
Using challenge is brought, the aqueous phase dispersibility for solving Graphene is a major challenge that chemist faces, for promoting its commercialization
It is great with research application value.
In order to solve the Aqueous dispersions sex chromosome mosaicism of Graphene, the method for most generally using is to introduce hydrophilic carboxylic on its surface
The groups such as base, hydroxyl, that is, substitute Graphene using graphene oxide (graphene oxide, GO).This method is true
Its aqueous phase dispersibility is improve in fact, but the lattice of Graphene is destroyed due to the introducing of these groups, thus cause Graphene
Electrical conductivity drastically declines several orders of magnitude, Graphene is changed into semiconductor from fabulous conductor.Recover the electric conductivity of Graphene,
Graphene oxide must be reduced to by Graphene by the mode such as complicated electronation or high temperature quenching, the complicated consumption of this process
When, and inevitably there is some faults of construction and then influence electrical conductivity in the Graphene of reduction.Document report by altogether
Valency mode functionalized graphite alkene improves its dispersed method, due to utilize the oxy radical of (oxidation) graphenic surface,
So as graphene oxide, electric conductivity is subject to extreme influence due to the presence of crystal structure defects.
The present invention has developed a kind of new method that water-soluble conducting Graphene is prepared using non-covalent fashion.Ionic liquid
It is a kind of to be made up of organic cation and organic or inorganic anion, at room temperature or close to the change that is in a liquid state completely at room temperature
Compound.Interacted using the π-π between Graphene and ionic liquid, will be with amphipathic characteristic (not only hydrophilic but also oleophylic, in water phase
With in organic phase all have certain solubility) ionic liquid hydrophobic graphenic surface is assembled into by non-covalent fashion, obtain
Must be through the ion liquid modified conductive graphene (slurries or solid form) with aqueous phase dispersibility with aqueous phase dispersibility.
Patents, hair are retrieved by patent network (official website such as China national Department of Intellectual Property, World Intellectual Property Organization)
Existing two patents property highest related to the present invention.One is CN201010287952, and it utilizes chemical method to pass through ionic liquid
Graphene oxide is modified；An another piece is CN201310675675, and it utilizes acidic ion liquid and alkali ionic liquid
As medium, Graphene is prepared by raw material of graphite powder by chemical method.Above-mentioned two patents are chemical methods, respectively with oxidation
Graphene and graphite powder are raw material, are related to redox etc. to chemically react, either method, raw material, the ionic liquid kind for using
The core contents such as class are unrelated with core content of the present invention, and the electrochemical sensor application example in the present invention is not related to yet.This
In invention the preparation method of water dispersible conductive graphene and obtain respective material, can be widely applied to electronic device, energy storage,
The fields such as sensing, catalysis.
The content of the invention
It is an object of the present invention to provide it is a kind of improve Graphene aqueous phase dispersibility, while again not to sacrifice the electric conductivity of Graphene
It is the short-cut method of cost.Easily directly can be modified as the Graphene of commercialization with water phase with non-covalent fashion by the method
The Graphene slurries or solid of dispersiveness, solve the Aqueous dispersions sex chromosome mosaicism of Graphene, while retaining intrinsic excellent of Graphene
Electric conductivity.Water present invention simultaneously relates to prepare mutually dispersibles application of the conductive graphene in fields such as electrochemical sensors.
Ionic liquid be it is a kind of be made up of organic cation and organic or inorganic anion, at room temperature or close to room temperature
Under the compound that is in a liquid state completely.Ionic liquid has excellent ionic conductivity, negligible vapour pressure (non-volatile because of it
Property), electrochemical window wide, chemically and thermally stability high, good dissolubility and be considered as being different from the green of conventional organic solvents
Solvent.Moreover, ionic liquid anion and cation type are various, various structures, can as needed carry out engineer
With ionic liquid of the synthesis with different physicochemical properties.With containing imidazoles (or pyridines) cation and amino acids anion
As a example by ionic liquid, [1- ethyl-3-methylimidazoles]+[alanine]-(english abbreviation：EMIMAla) and [1- ethyls-
3- methylimidazoles]+[1B]-(english abbreviation：EMIMPro), both ionic liquids all have hydrophilic, oleophylic two
Close property.Research in the past shows there is strong π-π phase interactions between the imidazole group and Graphene of glyoxaline ion liquid
With, using this strong interaction, add appropriate ionic liquid as modifying agent in water phase, it is subsequently adding a certain amount of stone
Black alkene ultrasound or concussion certain hour, you can by Ionic Liquid Modified to graphenic surface, the Graphene of surface hydrophobicity is modified
Into the Graphene of surface hydrophilic, the purpose that hydrophilic modifying is carried out to graphenic surface is reached.Additionally, after Ionic Liquid Modified
Graphene a large amount of electric charges due to surface band, are easier stabilization and deposit due to electrostatic repulsion between identical charges in water phase
.It is non-covalent modified through imidazoles amino acid ion liquid based on above-mentioned surface hydrophilic effect and Coulomb repulsion double action
Being dispersed in aqueous phase system of can stablizing of Graphene mutually dispersible Graphene (slurries or dispersible solid form) as water,
Simultaneously because Graphene lattice is not affected by destroying and remaining the intrinsic excellent conductivity of Graphene.
Relative to prior art, preparation method has the advantage that in the present invention：1) with traditional covalent bonding method phase
Than the non-covalent approach is simple and easy to do, can be prepared on a large scale.2), due to there is no any damage to Graphene lattice, so energy
Enough keep the intrinsic excellent electron electric conductivity of Graphene.3), compared with the dispersants such as surfactant, polymer, ionic liquid
With intrinsic ionic conductivity, so modified composite can introduce ionic conductivity, with more preferable electronics, ion
Composite conductive.4), transducer sensitivity, the reappearance between test limit, electrode batch built based on modified graphene material
All it is significantly improved etc. core capabilities index.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Transmission electron microscope (TEM) figure of Fig. 1 original graphite alkene
Fig. 2 .FT-IR spectrograms：Original graphite alkene (GR), graphene oxide (GO), ionic liquid EMIMAla, EMIMAla work(
The Graphene (GR-EMIMAla) of energyization
Fig. 3 shitosans (Chi), Graphene-shitosan (GR-Chi), graphene oxide-shitosan (GO-Chi), stone
The electrochemical impedance spectroscopy (Nyquist curves) of black alkene-ionic liquid-shitosan (GR-EMIMAla-Chi) modified electrode.It is real
Test condition:1mM K3[Fe(CN)6]/K4[Fe(CN)6] include 0.5M KNO3As supporting electrolyte, frequency range from 0.1Hz to
10kHz.Illustration:Randles equivalent simulation circuits.
The Graphene preparation process of Fig. 4 amino acid ion liquid functionalization and the assembling process then with enzyme molecule are former
Reason schematic diagram.
Fig. 5 are based on the bio-sensing that the Graphene (AAIL@GR) and graphene oxide (GO) of EMIMAla functionalization build
Typical ampere (current-vs-time) response curve and concentration correction curve of the device to catechol.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
The following is instrument and equipment used in the embodiment of the present invention of part, other not specific dated experiment conditions are pressed
More solito or the condition of instrument manufacturing factory suggestion.Fourier transform infrared spectrometry (FT-IR) instrument is Spectrum GX light
Spectrometer (Perkin--Elmer companies, the U.S.), transmission electron microscope instrument is JEM-2000EX (JEOL, Japan) with 120kV
As excitation voltage.Electrochemistry amperometric detection instrument is Shanghai Chen Hua electrochemical workstation CHI440, electrochemical impedance
Detection instrument is PGSTAT302N (Autolab, Switzerland).Electrochemical Detection uses three-electrode system, with the glass carbon for preparing
(GC) modified electrode is used as working electrode, using Ag/AgCl (3M KCl) as reference electrode, using platinum electrode as to electrode.With
Need to be by following pretreatment before in the glass-carbon electrode for preparing modified electrode：Respectively with 1.0,0.3,0.05 μm of three oxidations two
Aluminium powder polishes electrode surface, is then cleaned by ultrasonic 3 times repeatedly in absolute ethyl alcohol and deionized water, 1.5 minutes every time, then
It is standby glass-carbon electrode to be dried up with high pure nitrogen.Table 1 list 12 kinds for study ionic liquid (purity more than 98%).
1.12 kinds of table is used for the representative ionic liquid studied
The water of embodiment 1. mutually dispersibles the preparation of conductive graphene
It can be the Graphene of commercialization, or laboratory is homemade has to be used for modified Graphene in the present invention
The Graphene of high conductivity.A gives the transmission electron microscope picture (TEM) of original graphite alkene in Fig. 1.Due to the hydrophobic nature on surface,
In Graphene addition deionized water solution after shaking or be ultrasonic 15 minutes, Graphene still can be deposited on water phase bottom.Table 1
12 kinds are listed for the representative ionic liquid that Graphene is modified, cation is concentrated mainly on imidazoles, pyridines, phosphine,
Anion then covers amino acids, tetrafluoroborate, mesylate, hexafluorophosphate, fluoroform sulphonate, double (fluoroform sulphurs
Acyl) imines.The described dispersion slurries of the conductive graphene with aqueous phase dispersibility are preferably obtained in the following manner：By Graphene
Add in the mixed system of water and ionic liquid, dispersion is completed by ultrasound, stirring or concussion mode, acquisition is repaiied through ionic liquid
Decorations, be stably dispersed in aqueous phase system in graphene dispersion slurries；The described conductive graphene with aqueous phase dispersibility
By vacuum freeze drying or under 0-100 degrees Celsius of temperature conditionss, drying goes moisture removal to obtain to dispersion slurries；Described
Can Aqueous dispersions solid can by ultrasound or concussion etc. mode be re-dispersed into aqueous phase system, regain conductive graphene
Dispersion slurries；The described dispersion slurries of the conductive graphene with aqueous phase dispersibility include three kinds of water, Graphene and ionic liquid
Component, dispersible solid includes two kinds of components of Graphene and ionic liquid.
According to above-mentioned program, Graphene (the ratio between quality and water volume of Graphene can not be more than 10mg/ml) is added
In the mixed solution of the deionized water containing a certain amount of ionic liquid after shaking or be ultrasonic 15 minutes, the Aqueous dispersions of Graphene
Property because the ionic liquid that uses is different, difference is very big.0.4mg Graphenes are added in the aqueous solution of the 1ml containing ionic liquid,
The concentration of ionic liquid is general in 0.01mg ml-1To 20mg mL-1Between according to property and graphite such as the dissolubilities of ionic liquid
The dispersion effect of alkene is adjusted.Such as, 0.4mg ml are being contained-1GR and 3.0mg ml-1In the dispersion of ionic liquid, grind
Study carefully discovery, [1- ethyl -3- methyl the miaows with amphipathic characteristic (not only hydrophilic but also oleophylic has preferable solubility in water phase)
Azoles]+[alanine]-, [1- ethyl-3-methylimidazoles]+[L-PROLINE]-These amino acid ion liquids are in all researchs
Hydrophilic modifying in ionic liquid to Graphene has best effect.Modified through amino acid ion liquid, Graphene can
To be completely dispersed in aqueous and prolonged stability is kept, obtain the Graphene water being modified through amino acid ion liquid
Mutually disperse slurries.Above-mentioned slurries remove moisture removal by cryogenic vacuum freeze-drying or in the drying under 0 to 100 degrees Celsius
Afterwards, can obtain through the Graphene solid (Graphene and ionic liquid all keep down) of Ionic Liquid Modified, this solid is added
Can be again dispersed in water phase after ultrasound or concussion in water and obtain ion liquid modified graphene dispersion slurries.
Through same [1- ethyl-3-methylimidazoles] with amphipathic characteristic+[tetrafluoroborate]-It is modified, Graphene point
Scattered property makes moderate progress, and suspends in aqueous, but can not fully and completely disperse.Comparatively, amino acid ion liquid
Effect to improving Graphene aqueous phase dispersibility is well more many than tetrafluoro boron class.Completely hydrophobic ionic liquid, such as [trimethyl
(myristyl) phosphine]+[mesylate]-, [1- benzyl -3- methylimidazoles]+[hexafluorophosphate]-, as expected, to changing
The aqueous phase dispersibility of kind Graphene does not have positive effect.Other are used for the modified effect of modified ionic liquid between [1- second
Base -3- methylimidazoles]+[tetrafluoroborate]-With completely hydrophobic [trimethyl (myristyl) phosphine]+[mesylate]-Between,
Effect is not obvious.In sum, the amphiphilic ions liquid with imidazoles (or pyridines) cation and amino acids anion
Aqueous phase dispersibility of the body to improving Graphene in all ten several ionic liquids has best effect.Described amino acids
Anion includes 20 kinds of anion of natural amino acid；Described alkyl imidazolium cation includes imidazoles and in imidazole group
No. one and/or the substituted group R of third place (R formulas are CnH2n+1, and n is integer, the glyoxaline cation of 0≤n≤5)；Described
Pyridine cationoid include pyridine and on the N positions of pyridine substituted group R (R formulas are CnH2n+1, and n is integer, 0≤
The pyridylium of n≤5).There is imidazoles (or pyridines) very strong π-π to interact between cation and Graphene, graphite
Its hydrophobic surface becomes hydrophilic surface after alkene is modified through amino acid ion liquid；Additionally, through ion liquid modified graphite
The alkene surface band electric charge of many ionic liquids, each other in the presence of very strong electrostatic repulsion forces.The aqueous phase dispersibility of Graphene
Improvement be by the hydrophilic modifying on surface and both predominant intermolecular forces of Coulomb repulsion work to each other result.
The water of embodiment 2. mutually dispersibles the spectral characterization of conductive graphene
The water being modified through amino acid ion liquid mutually dispersibles Graphene has carried out table by spectroscopic methodology to its structure first
Levy.Fig. 2 gives original graphite alkene (GR), graphene oxide (GO), ionic liquid EMIMAla, and EMIMAla functionalization
The FT-IR spectrograms of Graphene (GR-EMIMAla).GR-EMIMAla samples for spectral characterization are to contain 0.2mg ml-1Graphite
Alkene and 0.25mg ml-1The modified graphene dispersion liquid of amino acid ion liquid sample after drying.Above-mentioned sample is by following
Mode is obtained：It is first-selected that 0.2mg Graphenes are added into 1ml ml containing 0.25mg-1In the water of EMIMAla ionic liquids, by ultrasound,
Stirring or concussion mode complete dispersion, obtain through Ionic Liquid Modified, be stably dispersed in aqueous phase system in Graphene point
Dissipate slurries；The above-mentioned dispersion slurries of the conductive graphene with aqueous phase dispersibility are taken the photograph by vacuum freeze drying or in 0-100
Drying goes moisture removal to obtain solid sample under the temperature conditionss of family name's degree.Control is it can be seen that Graphene and graphene oxide from figure
Between significant difference and ionic liquid to the modified effect of Graphene.Graphene oxide has substantial amounts of oxy radical, table
On present spectrogram, it is in 1055cm-1(C-O stretch peak), 1732cm-1(C=O), 1620cm-1(the skeleton shake of non-graphite oxide
Swing), 1221cm-1(C-OH stretch peak) place has obvious characteristic peak.The FT-IR spectrograms of Graphene are with graphene oxide very much not
Identical, the characteristic peak of most of oxy radicals observed on graphene oxide is disappeared on Graphene, and
1556cm-1Go out to have a characteristic peak for Graphene to occur, corresponding is the C=C keys concussion on graphene film sp2 carbon skeletons.From
Fig. 2 can be seen that after being modified through amino acid ion liquid, and the characteristic peak of nearly all ionic liquid EMIMAla and Graphene is all
Can be found in modified GR-EMIMAla nano composite materials, illustrate it is physics phase interaction between ionic liquid and Graphene
With rather than Covalently attached interaction.The characteristic absorption peak of EMIM [Ala] (namely acylamide II) is in 1576cm-1, ring type
EMIM+C-H vibrations appear in 1167cm-1And 623cm-1.And, it is relatively strong by 1405,843,3080cm on ionic liquid-1Absworption peak is appeared on GR-EMIMAla nano-complexes, illustrates that successfully Graphene table has been arrived in modification to ionic liquid
Face.On nano-complex the small displacement of the characteristic peak of ionic liquid EMIMAla illustrate simultaneously Graphene and ionic liquid it
Between have stronger interaction.In sum, from spectral characterization as can be seen that ionic liquid successfully hydrophilic changes to Graphene
Property be to be realized by non-covalent Physical interaction, the crystal structure of Graphene is not destroyed.
The electrochemical impedance spectroscopy that the water of embodiment 3. mutually dispersibles conductive graphene is characterized
The electric conductivity that the water being modified through amino acid ion liquid mutually dispersibles Graphene is carried out by electrochemical impedance spectroscopy
Characterize.The sharpest edges of graphene dispersion method used in the present invention are that it does not destroy the structure of Graphene, Neng Goubao
The intrinsic fabulous electron conduction of Graphene is held, this is that traditional covalent modification methods are not accomplished.This research is by electrification
Learn impedance method and investigated material modified heterogeneous electron (electric charge) and shift resistance (Rct), Rct can direct reaction material electric conductivity
Matter.Electrochemical impedance spectral method is a kind of very sensitivity for characterizing (the electricity of electronics between material and its surrounding ions, molecule
Lotus) exchange speed common tool.This electron exchange ability is closely related with the electric conductivity of material.If Graphene is through amino
Electric conductivity declines after the modification of acid ion liquid, can clearly be reflected in impedance spectrum result.Because Graphene, graphene oxide
The glass-carbon electrode (GC) that (water miscible) and modified graphene (GR-AAIL, water miscible) are individually modified is dipped into containing K3 [Fe
(CN) decorative layer can come off after the electrolyte solution of 6]/K4 [Fe (CN) 6] probe, all linear poly- with fine film forming ability
Compound shitosan (Chi) is used to fix decorative layer of the above-mentioned different materials to electrode surface to be stablized.Fig. 3 gives shell
Glycan (Chi), Graphene-shitosan (GR-Chi), graphene oxide-shitosan (GO-Chi), Graphene-ionic liquid
Body-shitosan (GR-EMIMAla-Chi) modified electrode is in 1mM K3[Fe(CN)6]/K4[Fe(CN)6] (include 0.5M KNO3Make
Be supporting electrolyte) in electrochemical impedance Nyquist (Nyquist) curve.Original solution for preparing modified electrode is
The pH6.5 phosphate buffers of the 10mM containing following component, concrete composition is as follows：GR-Chi/GC electrodes are ml containing 0.2mg-1GR and
0.3mg ml-1Chitosan solution, GO-Chi/GC is ml containing 0.2mg-1GO and 0.3mg ml-1Chitosan solution, GR-
EMIMAla-Chi/GC is ml containing 0.2mg-1GR,0.25mg ml-1EmimAla and 0.3mg ml-1Chitosan solution, Chi/GC
It is ml containing 0.3mg-1Chitosan solution.5 microlitres of above-mentioned solution is dripped into pretreated glassy carbon electrode surface, it is to be dried after obtain
Obtaining modified electrode is used to characterize.Its Randles equivalent simulation circuit is given in illustration simultaneously.In Nyquist impedance curves,
It is half diameter of a circle in the curve that measurement is obtained that charge transfer resistance (Rct) is corresponding.As can be seen from Figure 3, shitosan Chi tools
There is the Rct of maximum.Compared with Chi, the Rct of GO-Chi is reduced only by a bit, illustrate that the electric conductivity of GO is very poor.Because graphite oxide
There is substantial amounts of oxygen-containing functional group on alkene surface, and these groups destroy the structural intergrity and electron conduction of Graphene.But,
What GR-EMIMAla-Chi was presented is straight line, and Rct values are almost equal to zero, and illustrates that the interface electronics (electric charge) of this composite turns
Move resistance very small.This phenomenon demonstrates GR-EMIMAla has fabulous electric conductivity.The Nyquist figures of GR-EMIMAla-Chi
With the about the same of GR-Chi, illustrate that modifications of the EMIMAla to Graphene does not cause the electric conductivity of Graphene to occur declining.
Amino acid ion liquid has good ionic conductivity, it is possible to increase the charge transport capability of GR-EMIMAla composites.
Electrochemical impedance can be obtained with aqueous phase dispersibility it is demonstrated experimentally that be modified to Graphene by amino acid ion liquid
High conductivity Graphene, Graphene remains its intrinsic high conductivity.
Embodiment 4. is based on the biology sensor development of modified graphene and key property is characterized
The success of water-soluble graphene is prepared as traditional solution treatment technology (mistake that particularly biomolecule is participated in
Journey) provide convenience, in that context it may be convenient to develop graphene-based material and device.Different, the final ionic liquid according to experiment purpose
Can remain or get rid of with autotelic.Fig. 4 gives ionic liquid modified graphene and then and enzyme in water phase
Molecule (using tyrosinase Tyr as analogue enztme) assembling builds the principle schematic of electrochemica biological sensor.Graphene it is steady
The assembling process for determining Aqueous dispersions thing not only for enzyme molecule is most important, for improving the reappearance between enzyme electrode batch
It is most important.In research before, graphene oxide is usually used to replacement because having good aqueous phase dispersibility
Graphene.Sensor and be based on graphene oxide structure that this research builds the Graphene (AAIL@GR) being modified based on EMIMAla
The sensor built has carried out performance comparison.Original solution for preparing sensor is the pH6.5 phosphorus of the 10mM containing following component
Acid buffer, concrete composition is as follows：GR-EMIMAla-Tyr-Chi/GC is ml containing 0.2mg-1GR,0.25mg ml- 1EmimAla, 2.5mg/ml Tyr and 1.5mg ml-1Chitosan solution, GO-Tyr-Chi/GC sensors are ml containing 0.2mg- 1GO, 2.5mg/ml Tyr and 1.5mg ml-1Chitosan solution.By above-mentioned solution, 5 microlitres drip to pretreated glass-carbon electrode table
Face, it is to be dried after obtain GR-EMIMAla-Tyr-Chi/GC and GO-Tyr-Chi/GC sensors respectively.Two kinds of sensors are all used
To detect a kind of substrate catechol (important environmental contaminants) of tyrosinase, as shown in Figure 5.Biology based on AAIL@GR
Sensor test limit has reached 8nM, and the range of linearity has reached three orders of magnitude from 25nM to 11100nM, and the response time only needs to
3 seconds.It is worth mentioning that the sensitivity of the sensor has reached 12600mA cm-2M-1, than the sensing based on graphene oxide
Device sensitivity (736mA cm-2M-1) high 17 times.It is different from the graphene oxide that electrochemistry insulate, amino acid ion liquid function
The Graphene of change remains the intrinsic conductivity of Graphene, can be used for its substrate life of trapped enzyme electrode pair as electrochemistry wire
The signal of thing electro-catalysis, improves the sensitivity of sensor.The sensitivity of this sensor higher than it is reported in the literature based on Graphene,
The sensitivity of the sensor of the material constructions such as graphene oxide, CNT, mesoporous carbon.Compared with these traditional materials, ammonia
The Graphene of base acid ion liquid modifying has obvious advantage, be it is a kind of have very much prospect and with universality for developing
The platform of high sensitive electrochemical biology sensor.
Embodiment 5. is based on biology sensor reappearance, stability and the selective evaluation of modified graphene
The reappearance of sensor is studied by timing Amperometric.7 times continuous to 300nM catechols of biology sensor
The relative standard deviation (RSD) of detection is 2.6%, illustrates that sensor has good reappearance.In order to evaluate biology sensor
Reappearance between different batches electrode, 6 sensors are prepared for using same conditional sampling.The sensor of preparation it is relative
Standard deviation is 3.5%, illustrates there is good reappearance between sensor batch.The modified Graphene of amino acid ion liquid
With good aqueous phase dispersibility, this has played key effect for improving the reappearance between electrode and electrode.Some are common
Chaff interference is evaluated the influence that sensor is responded in the PBS of the pH7.0 of the catechol comprising 0.3 μM.Research finds
The organic matters such as ethanol, glucose, sucrose, uric acid and K+,Na+,Ca2+,NO3-,PO4-,Cl-,Ac-Inspection is not disturbed Deng inorganic matter
Survey.Due to tyrosinase in itself to substrate have well selectivity, and the detection current potential of this research institute it is very low (-
0.1V), so the external interference for introducing can be very small.Sensor sealing is placed in 4 DEG C of refrigerators and weekly using one to two
Secondary storage and stability in use for investigating sensor, after by five weeks, response electricity of the sensor to 300nM catechols
Stream is reduced only by 5%.Amino acid ion liquid is a kind of extraordinary ionic liquid of biocompatibility.Good long-term steady of sensor
It is qualitative to be mainly attributed to, for building the extraordinary biocompatibility of the nano-complex of sensor, one be provided for enzyme molecule
Individual favourable microenvironment prevents the inactivation of enzyme molecule.The excellent biocompatibility of amino acid ion liquid modified graphene and intrinsic
Good electric conductivity become biocompatibility construction enzyme base biology sensor fabulous platform.
Embodiment 6. is based on the biology sensor detection actual sample of modified graphene
The practicality of the biology sensor of development is evaluated by detecting environmental water sample.By adding catechol to river
The rate of recovery is tested in water (picking up from Liaoning Province Grand Liao River) and running water (picking up from Daliang City's running water).Water sample is first passed through
0.45 μm of filter filtering is with suspension of going out.In the range of 300nM to 10000nM additions, sensor detection running water and river
The rate of recovery between 90.5%to108.6%, RSD is between 2.2% to 6.0%.Illustrate that sensor can be used for actual sample
The detection of product, and with the extraordinary rate of recovery and standard deviation.
Claims (9)
1. a kind of mutually dispersible conductive graphene of water disperses slurries or solid, it is characterised in that：Using with aqueous phase dissolved degree
Ionic liquid hydrophilic modifying is carried out to conductive graphene by the physics mode of non-covalent bonding, obtaining has aqueous phase dispersibility
Conductive graphene dispersion slurries or can Aqueous dispersions solid；
The described ionic liquid with aqueous phase dissolved degree has imidazoles or pyridine cationoid and amino acids anion
Ionic liquid；
Described amino acids anion includes 20 kinds of anion of natural amino acid；Described alkyl imidazolium cation includes miaow
Azoles and in No. one of imidazole group and/or the glyoxaline cation of the substituted group R of third place, R formulas are CnH2n+1, n is whole
Number, 0≤n≤5；Described pyridine cationoid include pyridine and on the N positions of pyridine substituted group R pyridine sun from
Son, R formulas are CnH2n+1, n is integer, 0≤n≤5.
2. the mutually dispersible conductive graphene of water according to claim 1 disperses slurries or solid, it is characterised in that：
During conductive graphene added into the mixed system of water and ionic liquid, be well mixed obtain through Ionic Liquid Modified, can
It is stably dispersed in the conductive graphene dispersion slurries in aqueous phase system；The mixed system intermediate ion liquid and water of water and ionic liquid
Mass ratio be more than a ten thousandth；The ratio between mass fraction of system intermediate ion liquid and conductive graphene is more than 0.2；Or, will
Conductive graphene dispersion slurries drying goes moisture removal to obtain can Aqueous dispersions solid.
3. the mutually dispersible conductive graphene of water according to claim 2 disperses slurries or solid, it is characterised in that：
The mixed system intermediate ion liquid of water and ionic liquid is two 2 to percent/10000th with the mass ratio of water；
The ratio between mass fraction of system intermediate ion liquid and conductive graphene be 1 to 20 between.
4. the mutually dispersible conductive graphene of water according to claim 1 disperses slurries or solid, it is characterised in that：It is described
The ionic liquid with aqueous phase dissolved degree its solubility in pure water be more than a ten thousandth.
5. the mutually dispersible conductive graphene of water according to claim 1 disperses slurries or solid, it is characterised in that：
Mass-volume concentration (m/v) of the described conductive graphene in the mixed system of water and ionic liquid is more than zero and does not surpass
Cross 10mg/ml.
6. the mutually dispersible conductive graphene of water according to claim 1 disperses slurries or solid, it is characterised in that：
Mass-volume concentration (m/v) of the described conductive graphene in the mixed system of water and ionic liquid is arrived for 0.1mg/ml
2mg/ml。
7. the mutually dispersible conductive graphene of water according to claim 1 disperses slurries or solid, it is characterised in that：It is described
Conductive graphene be that 0.1s cm are more than by the electrical conductivity that either physically or chemically prepares-1Conductive graphene；Described is non-
The physics mode of covalent bonding does not cause to damage to the crystal structure of conductive graphene.
8. a kind of any conductive graphenes of claim 1-7 disperse the preparation method of slurries or solid, it is characterised in that：
The described dispersion slurries of the conductive graphene with aqueous phase dispersibility are obtained in the following manner：Conductive graphene is added
In the mixed system of water and ionic liquid, dispersion is completed by ultrasound, stirring or concussion mode, obtained through Ionic Liquid Modified
, be stably dispersed in aqueous phase system in conductive graphene dispersion slurries；The described electrically conductive graphite with aqueous phase dispersibility
By vacuum freeze drying or under 0-100 degrees Celsius of temperature conditionss, drying goes moisture removal to obtain to alkene dispersion slurries；It is described
Can Aqueous dispersions solid can by ultrasound or concussion mode be re-dispersed into aqueous phase system, regain conductive graphene
Dispersion slurries；The described dispersion slurries of the conductive graphene with aqueous phase dispersibility include water, conductive graphene and ionic liquid
Three kinds of components, can Aqueous dispersions solid bag two kinds of components containing conductive graphene and ionic liquid.
9. a kind of mutually dispersible conductive graphene dispersion slurries of any water of claim 1-7 or solid chemical sensitisation,
The application of bio-sensing, energy storage, device, catalysis or analysis field.
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| CN106928907B (en) * | 2017-02-23 | 2020-06-19 | 华南理工大学 | High-temperature stable nanofluid black liquor and preparation method and application thereof |
| CN111203288B (en) * | 2018-11-21 | 2022-07-26 | 中国科学院大连化学物理研究所 | Surface cation functionalized graphene oxide material, preparation and application |
| CN111354504A (en) * | 2020-03-13 | 2020-06-30 | 北京联研卓创科技有限公司 | Ionic liquid electric composite grease |
| CN111243780A (en) * | 2020-03-13 | 2020-06-05 | 北京联研卓创科技有限公司 | Graphene electric power composite grease |
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