CN108456288A - A kind of graphene-based Electrochemical Modification material of novel temperature-sensitive and its preparation method and application - Google Patents
A kind of graphene-based Electrochemical Modification material of novel temperature-sensitive and its preparation method and application Download PDFInfo
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- CRRUGYDDEMGVDY-UHFFFAOYSA-N CC(c1ccccc1)Br Chemical compound CC(c1ccccc1)Br CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- QZZBJCFNHPYNKO-UHFFFAOYSA-N CC(c1ccccc1)S Chemical compound CC(c1ccccc1)S QZZBJCFNHPYNKO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a kind of graphene-based Electrochemical Modification material of novel temperature-sensitive and its preparation method and application.The thermosensitive graphene based electrochemical decorative material is Fe (CN)6 3‑/ poly rGO, preparation method are：Under the action of AIBN, solvent is made with DMF, ionic liquid BVImBr and PNIPAM generate block copolymer poly (NIPAM b BVImBr)；Poly rGO are prepared using the π π non-covalent modifications effect between graphene and ionic liquid, Fe (CN) is synthesized by anion exchange reaction6 3‑/poly‑rGO.The Electrochemical Modification material scatter of preparation is preferable, while graphene reaches higher reducing condition, assign material Thermo-sensitive and ionic two kinds of intelligent responses, the material is applied in biosensor, it has expanded in electrochemical analysis, bio-sensing, electronic device, the application in the fields such as separating-purifying.
Description
Technical field
The present invention relates to field of nanocomposite materials, and in particular to a kind of graphene-based Electrochemical Modification material of novel temperature-sensitive
Expect Fe (CN)6 3-/ poly-rGO and preparation method thereof is applied.
Background technology
Biosensor is by bioactive substances such as enzyme, immune system, antibody, animal tissue, organelles as identification
Element is combined with physical chemistry converter, converts concentration to the detection device of electric signal.Biosensor is chemical sensitisation
One kind of device, has that high sensitivity, high efficiency, detection limit be low, specificly-response to object, and can be with on-line analysis very
To being in-vivo analysis, therefore cause great concern.
Graphene nanocomposite material shows good electron transport ability on electrochemica biological sensor, this makes
Graphene by very big concern and has potential using value in terms of Electrochemical enzyme biosensor.
Graphene is a kind of tightly packed carbonaceous new material at single layer bi-dimensional cellular shape lattice structure of carbon atom, is current
Until the most thin two-dimensional material that is found.It is well known that graphene has conductive capability strong, good biocompatibility and good
The advantageous properties such as chemical stability are widely used in the fields such as electrochemistry and material science.
However, there are stronger Van der Waals forces and π-π interactions, reduction process easily to send out between graphene sheet layer structure
Raw to reunite, this makes graphene receive certain limitation in very various applications.Graphene and other water solubilitys is good
Material be combined, prepare nanocomposite and can be very good to solve its dispersion problem in aqueous solution；In addition, graphite
Alkenyl nanocomposite may be incorporated into other functional materials, so as to assign graphene some characteristics.Function at present
There are many kinds of graphite alkene, and one of which is exactly the composite material that graphene is prepared with organic macromolecule.
In recent years, temperature-sensitive polymers are attracted widespread attention in the application of electrochemical field.Intellectual material is
The minor alteration of external environment (such as temperature, pH, salinity, light, magnetic field) can quickly be generated a kind of novel work(of response by referring to
It can property material.Poly-N-isopropyl acrylamide receives pass due to showing low critical solution temperature (LCST) in aqueous solution
Note.With the raising of aqueous temperature, intermolecular hydrogen bonding becomes intramolecular hydrogen bond, and phase separation occurs and generates precipitation, shows as
Hydrophobic state；When temperature is reduced to critical-temperature hereinafter, being reversibly restored to original hydrophilic extended configuration again.I.e. in phase transition
More than temperature, polymer chain, which caves in, shows as hydrophobicity, when in phase transition temperature hereinafter, polymer is stretched and is shown hydrophilic
Property, this hydrophobe-hydrophile state can repeat down always.
Graphene and intelligent macromolecule are such as compounded to form advanced composite material (ACM), graphene nano composite wood not only can be improved
Original basic performance is expected, it is also possible that graphene composite material has certain ambient intelligence response.
Invention content
An object of the present invention is to provide a kind of graphene-based electrification of novel temperature-sensitive with dual intelligent response
Learn decorative material Fe (CN)6 3-/poly-rGO。
The second object of the present invention is to provide a kind of graphene-based electrification of novel temperature-sensitive with dual intelligent response
Learn decorative material Fe (CN)6 3-The preparation method of/poly-rGO.
The third object of the present invention is to provide a kind of utilization Fe (CN)6 3-/ poly-rGO prepares electrochemical sensor Fe
(CN)6 3-/ poly-rGO/GC, this sensor not only save graphene original structure, also have changeable "ON" "Off"
Effect, and itself have it is electroactive, by studying the electrochemical behavior of the sensor at different temperatures, and to various concentration
Ascorbic acid detect.The result shows that this controllable electrochemical sensor is in electrochemical analysis, bio-sensing, electronics device
Part, the fields such as separating-purifying have higher application value.
The technical solution adopted by the present invention is：A kind of graphene-based Electrochemical Modification material of novel temperature-sensitive, described is new
Type thermosensitive graphene based electrochemical decorative material is Fe (CN)6 3-/poly-rGO。
A kind of preparation method of the graphene-based Electrochemical Modification material of novel temperature-sensitive, includes the following steps：First, in idol
Under the action of nitrogen bis-isobutyronitrile thermal initiator, using dimethylformamide as reflux solvent, ionic liquid 1- vinyl -3- butyl
Imidazoles bromide BVImBr and block copolymer PNIPAM generate block copolymer poly (NIPAM-b-BVImBr)；Then, it utilizes
π-π non-covalent modification effects between graphene and ionic liquid prepare polymerizate poly-rGO；Pass through anion exchange reaction
Synthesize thermosensitive graphene based electrochemical decorative material Fe (CN)6 3-/poly-rGO。
Above-mentioned preparation method, specially：
1) synthesis of block copolymer PNIPAM：By n-isopropyl acrylamide NIPAM, oxygen-ethyl dithiocarbonates
Dioxane, argon gas deoxygenation 30min is added after mixing in ethylo benzene and azodiisobutyronitrile AIBN, and oil bath temperature is set as 85
DEG C, it is heated to reflux 40h；Cooling, reactant is added dropwise in anhydrous ether by revolving, is filtered, and it is total to obtain block for vacuum drying
Polymers PNIPAM；
2) synthesis of block copolymer poly (NIPAM-b-BVImBr)：By 1- vinyl -3- butyl imidazole bromides
After mixing, dimethylformamide DMF, argon gas deoxygenation 30min is added in BVImBr, PNIPAM and azodiisobutyronitrile AIBN,
Oil bath temperature is set as 85 DEG C, is heated to reflux 40h；It is cooling, reactant is added dropwise in anhydrous ether, is filtered, it is dry, it obtains embedding
Section copolymer poly (NIPAM-b-BVImBr)；
3) synthesis of compound poly-rGO：By appropriate graphene oxide GO powder and water, after ultrasonic disperse, block is added
Copolymer poly (NIPAM-b-BVImBr), hydrazine hydrate is added after dissolving, obtains mixed solution, and oil bath temperature is set as 110 DEG C, mixing
After solution heating reflux reaction 40h, upper solution is taken after cooling, is freeze-dried, obtains compound poly-rGO；
4) Electrochemical Modification material Fe (CN)6 3-The synthesis of/poly-rGO：Take compound poly-rGO and K3[Fe(CN)6]
It is dissolved in deionized water respectively, after equal ultrasonic disperse is at solution respectively, by K3[Fe(CN)6] solution is added dropwise to poly-rGO
In solution, reaction is stirred at room temperature for 24 hours, washs, freeze-drying obtains Fe (CN)6 3-/poly-rGO。
Above-mentioned preparation method, in step 1), n-isopropyl acrylamide NIPAM, oxygen-ethyl dithiocarbonates ethyl
The ratio between amount of substance of benzene and azodiisobutyronitrile AIBN is 48-52:1:0.03-0.07.
Above-mentioned preparation method, in step 2), 1- vinyl -3- butyl imidazole bromides BVImBr, PNIPAM and azo two
The ratio between amount of substance of isobutyronitrile AIBN is 78-82:1:0.13-0.17
Above-mentioned preparation method, in step 3), the mass ratio of GO and Poly (NIPAM-b-BVImBr) is 1:18-22.
Above-mentioned preparation method in step 3), after hydrazine hydrate is added, adjusts the pH value of mixed solution between 9-10.
Application of the graphene-based Electrochemical Modification material of novel temperature-sensitive in electrochemical sensor.The electrochemistry passes
Sensor is by the above-mentioned graphene-based Electrochemical Modification material Fe (CN) of novel temperature-sensitive6 3-/ poly-rGO is coated on glass-carbon electrode
On GC, it is prepared into Fe (CN)6 3-/ poly-rGO/GC modified electrodes.
Fe(CN)6 3-Application of/poly-rGO/GC the modified electrodes in Electrochemical Detection ascorbic acid.
The present invention is mainly acted on using the π-π non-covalent modifications between graphene and ionic liquid to prepare graphene nano
Composite material, prepare by the method for the invention graphene nanocomposite material dispersibility preferably, and graphene reach compared with
While high reducing condition, material Thermo-sensitive and both ionic intelligent responses are imparted so that graphene composite material
On the basis of improving original basic performance, certain environment-responsive has been had both, has been prepared for composite material poly-rGO, and right
Its pattern, structure, property are characterized.Since ionic liquid has ion exchangeable so that composite material has dual
Intelligent response passes through the graphene-based functional material Fe (CN) of anion exchange reaction synthesis of electroactive6 3-/ poly-rGO,
It can be applied to electrochemical analysis, bio-sensing, electronic device, the fields such as separating-purifying.
The graphene-based electrochemical sensor of novel temperature-sensitive prepared by the present invention has Thermo-sensitive and ionic.It can apply
In electrochemical analysis field.
The invention has the advantages that：
1, the graphene-based electrochemical sensor Fe (CN) of novel temperature-sensitive of the invention6 3-/ poly-rGO/GC, it is mainly sharp
It is acted on the π-π non-covalent modifications between graphene and ionic liquid to prepare graphene nanocomposite material, passes through party's legal system
Standby graphene nanocomposite material dispersibility preferably, and while graphene reaches higher reducing condition, imparts material
Expect Thermo-sensitive and both ionic intelligent responses so that graphene composite material is on the basis for improving original basic performance
On, intelligent response is had both, when temperature and solion change, reversible change occurs for solution hydrophilic and hydrophobic.
2, the present invention is prepared for having temperature sensitive using the unique ion exchangeable of ionic liquid by ion-exchange reactions
The graphene-based electrochemical sensor Fe (CN) of property6 3-/poly-rGO/GC.It is proved by electrochemistry experiment, Fe (CN)6 3-/poly-
RGO/GC can be used as the controllable detection that intelligent response electrochemical sensor realizes Ascorbic Acid.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of GO (a) and poly-rGO (b).
Fig. 2 is the photo of GO (a), rGO (b) and poly-rGO (c) dispersions in aqueous solution.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of GO (a), rGO (b) and poly-rGO (c).
Fig. 4 is the infrared spectrogram (FT-IR) of rGO (a), poly (NIPAM-b-BVImBr) (b) and poly-rGO (c).
Fig. 5 a are the x-ray photoelectron spectroscopy figure of GO.
Fig. 5 b are the x-ray photoelectron spectroscopy figure of rGO.
Fig. 5 c are the x-ray photoelectron spectroscopy figure of poly-rGO.
Fig. 5 d are Fe (CN)6 3-The x-ray photoelectron spectroscopy figure of/poly-rGO.
Fig. 6 is poly-rGO in 20 DEG C (a), 45 DEG C (b) and digital photograph when reforming into 20 DEG C (c).
Fig. 7 is that poly-rGO in 20 DEG C (a), 45 DEG C (b) and reforms into the ultravioletvisible absorption of 20 DEG C (c) respectively
Spectrogram.
Fig. 8 is Thermo-sensitive cycle figures of the poly-rGO at 20 DEG C and 45 DEG C.
Fig. 9 is Fe (CN)6 3-The cyclic voltammetry curve comparison diagram of/poly-rGO/GC (a) and poly-rGO/GC (b).
Figure 10 is Fe (CN)6 3-The cyclic voltammetric of/poly-rGO/GC 50 circles of scanning in PBS buffer solutions (pH=7) is bent
Line.
Figure 11 is Fe (CN)6 3-/ poly-rGO/GC continuous scannings 50 enclose the corresponding peak current trend chart of cyclic voltammetric.
Figure 12 is Fe (CN)6 3-The cyclic voltammetric that/poly-rGO/GC is scanned in the PBS of 20 DEG C (a) and 45 DEG C (b) is bent
Line.
Figure 13 is Fe (CN)6 3-/ poly-rGO/GC temperature sensitivity response cycle figures in PBS (pH=7).
Figure 14 is Fe (CN)6 3-/ poly-rGO/GC is in PBS (pH=7) (a) and PBS (pH containing 0.15mM ascorbic acid
=7) cyclic voltammetry curve of (b).
Figure 15 is Fe (CN)6 3-The I-T curves of/poly-rGO/GC Ascorbic Acids.
Figure 16 is Fe (CN)6 3-/ poly-rGO/GC is to corresponding ascorbic acid concentrations calibration curve.
Specific implementation mode
Technical solution for a better understanding of the present invention, spy are described in further detail with specific embodiment, but side
Case is without being limited thereto.
The graphene-based Electrochemical Modification material Fe (CN) of 1 novel temperature-sensitive of embodiment6 3-/poly-rGO
(1) synthesis of oxygen-ethyl dithiocarbonates ethylo benzene
The accurate 0.80g oxygen-ethyl dithiocarbonates sylvite that measures is dissolved in 50 DEG C of ethyl alcohol of 10mL, is added at this temperature
Enter 1.0g (1- bromoethyls) benzene, stir 2.5h, 30mL deionized waters are added, are extracted with ether, organic extract through dry filter,
Solvent is removed, obtains yellow oil, as oxygen-ethyl dithiocarbonates ethylo benzene.
(2) synthesis of ionic liquid 1- vinyl -3- butyl imidazoles bromide (BVImBr)
The bromobutane and 30mL methanol for measuring 9.41g 1- vinyl imidazoles, 16.68g, sequentially add into round-bottomed flask,
It is heated to reflux 15h, the temperature setting of reaction is to 60 DEG C.Stop reaction postcooling to room temperature, reactant is poured into beaker, is used
Acetonitrile-re-crystallizing in ethyl acetate is dried in vacuo after filtering, obtains white solid powder, as ionic liquid 1- vinyl -3- fourths
Base imidazoles bromide (BVImBr).
(3) purifying of n-isopropyl acrylamide
NIPAM (n-isopropyl acrylamide) monomer for weighing 10.0020g is added in two mouthfuls of round-bottomed flasks of 200ml,
Heating is added dropwise acetone and is all dissolved to NIPAM, and n-hexane, the acetone of addition and the amount of n-hexane its volume is added dropwise in cooling for reflux
Than being about 1:6, stop heating.It is transferred in refrigerator after being cooled to room temperature.After crystal precipitation after, take out filter, be used in combination n-hexane into
Row washing.Be put into after vacuum drying at room temperature in drier store it is spare.
(4) synthesis of block copolymer PNIPAM
Accurately weigh 6.4048g n-isopropyl acrylamide (NIPAM), oxygen-ethyl dithiocarbonates of 0.2536g
The azodiisobutyronitrile (AIBN) of ethylo benzene and 0.0092g, is added in 100ml round-bottomed flasks, then 30mL bis- is added thereto
Oxygen hexane, argon gas deoxygenation 30min, then in the state of stirring, oil bath is heated at reflux 40h, and oil bath temperature is set as 85 DEG C.Reaction
After be cooled to room temperature, reaction product is rotated, the extra dioxane in part is removed, then adds reactant dropwise
Entering into the anhydrous ether of 200mL, can be observed have white precipitate precipitation, filters, vacuum drying obtains white solid powder,
As block copolymer PNIPAM.
(5) synthesis of block copolymer poly (NIPAM-b-BVImBr)
The accurate 1- vinyl -3- butyl imidazoles bromides (BVImBr) for weighing 0.1836g, the PNIPAM of 0.5081g and
The azodiisobutyronitrile (AIBN) of 0.0025g, is added in 100ml round-bottomed flasks, then 30mL dimethyl formyls are added thereto
Amine (DMF), argon gas deoxygenation 30min are heated to reflux 40h, and oil bath temperature is set as 85 DEG C.Reaction terminates liquid nitrogen cooling, makes quickly to stop
Only, solvent is removed, then reactant is added dropwise in the anhydrous ether of 200mL, can be observed have pale yellow precipitate precipitation,
Filtering, vacuum drying, obtains faint yellow solid powder, i.e. block copolymer poly (NIPAM-b-BVImBr).
(6) preparation of graphene oxide GO
It is added in three neck round bottom flask after the concentrated sulfuric acid of 67.5mL is accurately measured, and round-bottomed flask is put in ice-water bath
The NaNO of 2.0051g high purity graphites and 1.6057g is added into system for middle holding low temperature3, slowly will after stirring evenly
9.0125g KMnO4Solid is added in round-bottomed flask, and drug is added and needs that the temperature in flask is kept to maintain always in the process
5 DEG C hereinafter, being then heated to 35 DEG C after react 30min.When reaction closes on terminal, it is sticky that black suspension becomes taupe
Object, then place one week at room temperature.It finally uses the hot water of 560.0mL to dilute, 3% H is added dropwise2O2Unreacted manganese ion is restored,
H is added dropwise2O2Until becoming glassy yellow.With the NaOH centrifuge washings of a concentration of 0.01M to neutrality, then with deionized water centrifuge washing,
Remove SO4 2-, it is examined with saturation barium acetate, washing finally can be used ethyl alcohol to wash twice until no longer generating white precipitate,
Vacuum drying obtains graphene oxide GO, spare.
(7) synthesis of redox graphene rGO
The graphene oxide GO powder for weighing 0.005g is added in the round-bottomed flask of 100mL, then 10mL is added thereto
Water, ultrasonic disperse GO dissolvings, is added ammonium hydroxide 10mL, stirs the hydrazine hydrate of addition 1mL after 30min.It is heated at reflux reaction for 24 hours, oil
The temperature of bath heating is set as 110 DEG C.After stopping heating, cooling and standings.After taking upper solution to be freeze-dried, reduction-oxidation graphite is obtained
Alkene rGO, it is spare.
(8) synthesis of compound poly-rGO
The graphene oxide GO powder for weighing 0.005g is added in the round-bottomed flask of 100mL, then 10mL is added thereto
After ultrasonic disperse 30min, 1.0500g block copolymers poly (NIPAM-b-BVImBr) is added in water, fully after oscillation dissolving,
The hydrazine hydrate that 5mL is added into round-bottomed flask, obtains mixed solution, adjusts the pH value of mixed solution between 9-10.Reflux adds
The temperature of thermal response 40h, oil bath heating are set as 110 DEG C.One day is stood after stopping heating, after taking upper solution to be freeze-dried, is obtained
Compound poly-rGO, it is spare.
Structure and the characterization of pattern are carried out to the poly-rGO of synthesis, correlated results is as shown in Figs 1-4.
In Fig. 1, b is the transmission electron microscope picture of poly-rGO, is observed by TEM electron microscopes, pattern and the GO phases of poly-rGO
Than significant change does not occur, is irregular laminated structure, and there is a large amount of fold on surface.
In Fig. 2, c is the photo figure of poly-rGO dispersions in aqueous solution, as shown, due to being compounded with ionic liquid,
The water solubility of redox graphene is substantially increased, thus the poly-rGO aqueous solutions of compound are macroscopically showing as disperseing
The good dark solution of property.
In Fig. 3, c is the ultraviolet-visible absorption spectroscopy figure of compound poly-rGO, by figure it can be seen that having in 273nm
The characteristic peak of rGO shows that compound has obtained abundant reduction.
Fig. 4 is characterized to the structure of compound using FT-IR, and curve a is the infrared spectrum curve of rGO, and b is
Poly (NIPAM-b-BVImBr) infrared spectrum curve, c are that the infrared spectrum curve of compound poly-rGO is repaiied as seen from the figure
The graphene of decorationsization is in 1458cm-1And 1544cm-1The characteristic peak that place occurs is the characteristic absorption peak of C=C on imidazole ring,
1649cm-1The absorption peak at place belongs to secondary amide C=O stretching vibration absworption peaks, 1366cm in PNIPAM-1And 1387cm-1Place
Absorption peak belong to C-N stretching vibrations absorb and N-H bending vibrations absorb characteristic peak.It can be seen that compared with rGO, warp
Graphene nanometer sheet after reduction treatment contains the amide on imidazole ring and macromolecular chain, it is possible thereby to be inferred on graphene
Introduce compound poly (NIPAM-b-BVImBr).
(9) Electrochemical Modification material Fe (CN)6 3-The synthesis of/poly-rGO
Electrochemical Modification material Fe (CN)6 3-/ poly-rGO is by synthesized by simple anion exchange reaction.It takes
The compound poly-rGO of 0.05g step (8) synthesis is dissolved in the deionized water of 7mL, then weighs the K of 0.15g3[Fe
(CN)6] be dissolved in the deionized water of 3mL, after both ultrasonic disperse is at solution, by K3[Fe(CN)6] solution is added dropwise to
In poly-rGO solution.After being stirred at room temperature 24 hours, mixture is washed for several times with the deionized water of heat.Finally, it freezes
After drying, Electrochemical Modification material Fe (CN) is obtained6 3-/poly-rGO。
Fig. 5 a- Fig. 5 b are respectively GO, rGO, poly-rGO and Fe (CN)6 3-The x-ray photoelectron spectroscopy figure of/poly-rGO.
Pass through Fig. 5 a, it can be seen that occur the characteristic peak of C1s and O1s respectively at 287.0eV and 543.55eV.In contrast, scheme
In 5b, the peak height of O1s is greatly lowered compared with Fig. 5 a, to illustrate that GO is reduced.As can be seen that compound poly- in Fig. 5 c
RGO occurs belonging to the track characteristic peak of Br3d and N1s at 98.9eV and 396.8eV respectively, is compared by contained element
Analysis can be inferred that the present invention has successfully introduced block copolymerization poly (NIPAM-b-BVImBr) on graphene.Profit
With Fe (CN)6 3-Ion-exchange reactions is carried out with poly-rGO, Fig. 5 d are functional material Fe (CN)6 3-The X of/poly-rGO is penetrated
There is the track characteristic peak of Fe2p at 708.2eV in photoelectron spectra, illustrates successfully to have synthesized functional material Fe
(CN)6 3-/ poly-rGO, to prove that it is good ionic that poly-rGO has.
Embodiment 2
(1) compound poly-rGO Thermo-sensitives are examined
The compound poly-rGO aqueous solutions for taking 1 step (8) of embodiment of 10ml to prepare, are put into the sample bottle of 15ml,
60 DEG C of degree heating 5min of water-bath, observation experiment phenomenon, it is possible to find the former preferable dark solution of dispersibility gradually becomes black turbid,
Black precipitate is ultimately generated, is stood, upper layer is colourless transparent solution in sample bottle, and lower layer is black precipitate.Restore to room temperature,
It gently shakes sample bottle black precipitate to disappear, and becomes the preferable dark solution of dispersibility, it is specific as shown in Figure 6.Fig. 6 is
Poly-rGO aqueous solutions are in 20 DEG C (a), 45 DEG C (b) and digital photograph when reforming into 20 DEG C (c), it will be appreciated from fig. 6 that multiple
Closing object poly-rGO has good Thermo-sensitive.
Fig. 7 be poly-rGO aqueous solutions respectively 20 DEG C (a), 45 DEG C (b) and reform into the ultraviolet of 20 DEG C (c) can
See abosrption spectrogram, as seen from the figure, 20 DEG C of compound has a characteristic absorption peak at 273nm, after increasing the temperature to 45 DEG C,
Due to the variation of PNIPAM hydrophilic and hydrophobics, generates black polymer and sink to bottom, the characteristic peak at 273nm is caused to disappear, when weight
After being newly restored to 20 DEG C, hydrophily changes again, becomes the solution of former favorable dispersibility again, occurs at 273nm special
Peak is levied, thus further proves that the compound poly-rGO of synthesis has good Thermo-sensitive, and circulating and reversible, embodies
"ON" "Off" effect.
(2) the temperature sensitive reversible ultraviolet tests of compound poly-rGO
In the compound that wavelength is 1 step (8) of embodiment preparation under the conditions of the places 273nm survey 45 DEG C of 20 DEG C of room temperature and high temperature
The absorbance value of poly-rGO aqueous solutions, room temperature → high temperature → room temperature → high temperature, iterative cycles are tested ten times, due under high temperature,
Hydrophobic state is presented in compound poly-rGO, and absorbance is approximately 0, becomes hydrophily, circulating and reversible again after restoring room temperature.
As shown in figure 8, Thermo-sensitives of the poly-rGO at 45 DEG C of 20 DEG C of room temperature and high temperature recycles figure, when temperature at 20 DEG C and
When changing between 45 DEG C, since compound poly-rGO shows as hydrophilic → hydrophobic → hydrophilic state, in ultra-violet absorption spectrum
Peak → without peak → is then shown in curve the variation at peak.The compound poly-rGO synthesized as shown in Figure 8 has Thermo-sensitive,
And circulating and reversible has preferable "ON" "Off" effect.
(3) Fe (CN)6 3-The preparation of/poly-rGO/GC
1, the pretreatment of glass-carbon electrode
This experiment uses the glass-carbon electrode of a diameter of 3mm, respectively with 1.0,0.3,0.05 μm of Al2O3To glass-carbon electrode into
Row polishing is cleaned by ultrasonic 1min with ultra-pure water.With glass-carbon electrode (GC) for working electrode, platinum filament is to electrode, Ag/AgCl electrodes
For reference electrode, three-electrode system is constituted.In 1mM K3Fe(CN)61M KCl solution in carry out electrochemistry cyclic voltammetric (CV)
Test, scanning range -200-800mV (vs.Ag/AgCl), sweep speed 200mV/s.Oxidation peak when electrode and reduction
When the peak position difference at peak is less than 70.0mV, illustrate that the electrode reaches the requirement of activation clean.Glass-carbon electrode is taken out, it is clear with ultra-pure water
It washes, high pure nitrogen (N2) drying it is spare.
2、Fe(CN)6 3-The preparation of/poly-rGO/GC
The Fe (CN) for taking 7.0 μ L embodiments 1 to prepare6 3-The solution of/poly-rGO, drop coating to the glass-carbon electrode pre-processed
Surface, one drying of mask and clean beaker, are dried for 24 hours, moisture slow evaporation, in electrode surface shape at room temperature on the electrode
At thin film to get to Fe (CN)6 3-/ poly-rGO/GC modified electrodes.
This experiment is in the PBS buffer solutions of 0.1M pH=7.Using three-electrode system, Ag/AgCl electrodes are reference electricity
Pole, platinum electrode are auxiliary electrode, Fe (CN)6 3-/ poly-rGO/GC modified electrodes are working electrode.
(4) Fe (CN)6 3-The electrochemical Characterization of/poly-rGO/GC is tested
When electrochemical Characterization is tested, this experiment is in the buffer solution of 0.1M pH=7.0, to sweep the item of fast 200mV/s
Under part.Using three-electrode system, Ag/AgCl electrodes are reference electrode, and platinum electrode is auxiliary electrode, respectively with Fe (CN)6 3-/
Poly-rGO/GC and poly-rGO/GC modified electrodes are working electrode.Under identical experiment condition, Fe (CN)6 3-/poly-
RGO/GC modified electrodes enclose for working electrode continuous scanning 50, detect the stability and applicability of its electrode material.
From Fig. 9, curve a and b is it is observed that compared with poly-rGO/GC (b), Fe (CN)6 3-/poly-rGO/GC
(a) it is respectively that -2.418 μ A and 3.334 μ A, peak position are poor to have the good redox peaks of a pair of of invertibity, redox current
For 75mV, and it is corresponding with redox peaks of the potassium ferricyanide in identical environment, this illustrates that iron cyanogen root is successfully supported on
Electrode surface so that composite material shows electroactive feature in Electrochemical Detection.
From, as it can be seen that after the circle of continuous scanning 50, peak current changes within 5%, this illustrates electrification in Figure 10 and Figure 11
Learn sensor Fe (CN)6 3-/ poly-rGO/GC is with good stability, can be used as electrochemical sensor.
(5) Fe (CN)6 3-Temperature sensitive reversible electrochemistry cyclic voltammetry of/poly-rGO/GC modified electrodes
In temperature sensitive reversible electrochemistry cyclic voltammetry, in the buffer solution of 0.1M pH=7.0, to sweep speed
Under conditions of 200mV/s.Using three-electrode system, Ag/AgCl electrodes are reference electrode, and platinum electrode is auxiliary electrode, Fe
(CN)6 3-/ poly-rGO/GC and poly-rGO/GC modified electrodes are working electrode, respectively under 20 DEG C and 45 DEG C of two temperature,
Electrochemical cyclic voltammetry carries out the cycle detection of two temperature.
In Figure 12, Fe (CN)6 3-There is a pair of reversible redox peaks, redox electricity at 20 DEG C in/poly-rGO/GC
Stream is respectively -2.385 μ A and 3.295 μ A, and peak position difference is 72mV, and peak current illustrates the electron-transport in electrode surface with peak position difference
Better performances show as "open" state.However when temperature is increased to 45 DEG C, prodigious change has occurred in cyclic voltammetric signal
Change, peak current reduces, and the redox peaks of the potassium ferricyanide disappear, and the electronic transmission process of electrode surface is completely blocked, and show
For "off" state.The result shows that this modified electrode declines with the raising electron transport ability of temperature, thus it is speculated that this is because temperature
Degree increases, since poly-rGO chains collapse, to hinder the transmission of electronics.
Shown in Figure 13, comparison it is found that when temperature 20 DEG C and 45 DEG C repetition transformation when, Fe (CN)6 3-/ poly-rGO/GC is still
Original circulating and reversible temperature sensitive intelligent response is maintained well.It is embodied in the invertibity of peak current, and this reversible
Transformation can repeat down well always.Hence it is demonstrated that Fe (CN)6 3-/ poly-rGO can be used as thermosensitive graphene base
Electrochemical sensor.
(6) Fe (CN)6 3-The electro-catalysis response of/poly-rGO/GC modified electrode Ascorbic Acids is probed into
It utilizes Fe (CN)6 3-/ poly-rGO/GC modified electrodes Ascorbic Acid has carried out Electrochemical Detection.Such as Figure 14 institutes
Show, after 0.15mM ascorbic acid is added, cathode peak is progressively smaller until disappearance.Illustrate that allusion quotation has occurred in potassium ferricyanide Ascorbic Acid
The electrocatalytic reaction of type.
(7) Fe (CN)6 3-The detection of/poly-rGO/GC modified electrode Ascorbic Acids
Fe(CN)6 3-/ poly-rGO/GC modified electrodes are bent to the current-responsive for being continuously added to the ascorbic acid of various concentration
Line detects under the premise of not changing three-electrode system, tests Fe (CN)6 3-/ poly-rGO/GC modified electrodes are in PBS (pH=
7.0) the I-T curves in.
As can be seen from Figure 15, Fe (CN)6 3-/ poly-rGO/GC modified electrodes are in ascorbic acid concentrations ranging from 30 μ
With reduction peak current in good linear relationship in M -0.3mM, equation of linear regression is y=-0.006x-0.1517 (R=
0.997, n=13), detection is limited to 5 μM (S/N).
It is 85.6mA ﹒ cm according to the sensitivity of the slope modified electrode of Figure 16 calibration curve cathetus-2﹒ M-1。Fe
(CN)6 3-The detection limit of/poly-rGO/GC modified electrode Ascorbic Acids is relatively low, and sensitivity is relatively high.
Claims (10)
1. a kind of graphene-based Electrochemical Modification material of novel temperature-sensitive, which is characterized in that the novel temperature-sensitive graphene
Based electrochemical decorative material is Fe (CN)6 3-/poly-rGO。
2. a kind of preparation method of the graphene-based Electrochemical Modification material of novel temperature-sensitive described in claim 1, feature exist
In including the following steps：First, molten using dimethylformamide as flowing back under the action of azodiisobutyronitrile thermal initiator
Agent, ionic liquid 1- vinyl -3- butyl imidazole bromide BVImBr and block copolymer PNIPAM generate block copolymer poly
(NIPAM-b-BVImBr)；Then, polymerizate is prepared using the π-π non-covalent modification effects between graphene and ionic liquid
poly-rGO；Finally by anion exchange reaction synthesis thermosensitive graphene based electrochemical decorative material Fe (CN)6 3-/poly-
rGO。
3. preparation method according to claim 2, which is characterized in that be specially：
1) synthesis of block copolymer PNIPAM：By n-isopropyl acrylamide NIPAM, oxygen-ethyl dithiocarbonates ethyl
After mixing, dioxane, argon gas deoxygenation 30min is added in benzene and azodiisobutyronitrile AIBN, and oil bath temperature is set as 85 DEG C, adds
Heat reflux 40h；Cooling, reactant is added dropwise in anhydrous ether by revolving, is filtered, and vacuum drying obtains block copolymer
PNIPAM；
2) synthesis of block copolymer poly (NIPAM-b-BVImBr)：By 1- vinyl -3- butyl imidazole bromides BVImBr,
After mixing, dimethylformamide DMF, argon gas deoxygenation 30min, oil bath temperature is added in PNIPAM and azodiisobutyronitrile AIBN
85 DEG C are set as, 40h is heated to reflux；It is cooling, reactant is added dropwise in anhydrous ether, is filtered, it is dry, obtain block copolymer
poly(NIPAM-b-BVImBr)；
3) synthesis of compound poly-rGO：By appropriate graphene oxide GO powder and water, after ultrasonic disperse, block copolymerization is added
Object poly (NIPAM-b-BVImBr) is added hydrazine hydrate and obtains mixed solution after dissolving, oil bath temperature is set as 110 DEG C, mixed solution
Heating reflux reaction 40h takes upper solution to be freeze-dried, obtains compound poly-rGO after cooling；
4) Electrochemical Modification material Fe (CN)6 3-The synthesis of/poly-rGO：Take compound poly-rGO and K3[Fe(CN)6] respectively
It is dissolved in deionized water, after equal ultrasonic disperse is at solution respectively, by K3[Fe(CN)6] solution is added dropwise to poly-rGO solution
In, reaction is stirred at room temperature for 24 hours, washs, freeze-drying obtains Fe (CN)6 3-/poly-rGO。
4. preparation method according to claim 3, which is characterized in that in step 1), n-isopropyl acrylamide NIPAM,
The ratio between amount of substance of oxygen-ethyl dithiocarbonates ethylo benzene and azodiisobutyronitrile AIBN is 48-52:1:0.03-0.07.
5. preparation method according to claim 3, which is characterized in that in step 2), 1- vinyl -3- butyl imidazole bromides
The ratio between amount of substance of BVImBr, PNIPAM and azodiisobutyronitrile AIBN is 78-82:1:0.13-0.17.
6. preparation method according to claim 3, which is characterized in that in step 3), GO and Poly (NIPAM-b-
BVImBr mass ratio) is 1:18-22.
7. preparation method according to claim 3, which is characterized in that in step 3), after hydrazine hydrate is added, it is molten to adjust mixing
The pH value of liquid is between 9-10.
8. application of the graphene-based Electrochemical Modification material of novel temperature-sensitive described in claim 1 in electrochemical sensor.
9. application according to claim 8, which is characterized in that the electrochemical sensor is will be described in claim 1
The graphene-based Electrochemical Modification material Fe (CN) of novel temperature-sensitive6 3-/ poly-rGO is coated on glass-carbon electrode GC, is prepared into Fe
(CN)6 3-/ poly-rGO/GC modified electrodes.
10. application according to claim 9, which is characterized in that Fe (CN)6 3-/ poly-rGO/GC modified electrodes are in electrification
Learn the application in detection ascorbic acid.
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| CN108862245A (en) * | 2018-04-27 | 2018-11-23 | 辽宁大学 | A kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation method and application |
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN113461856A (en) * | 2021-07-02 | 2021-10-01 | 辽宁大学 | Gel material with electrochemical activity and temperature sensitivity and preparation method and application thereof |
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| EP2583940A1 (en) * | 2011-10-21 | 2013-04-24 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Stabilization of carbon nanomaterials and hydrophobic compounds by copolymers |
| CN105860403A (en) * | 2016-06-01 | 2016-08-17 | 辽宁大学 | Graphene nano composite material with dual intelligent responsivities |
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| CN105860403A (en) * | 2016-06-01 | 2016-08-17 | 辽宁大学 | Graphene nano composite material with dual intelligent responsivities |
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| CN108862245A (en) * | 2018-04-27 | 2018-11-23 | 辽宁大学 | A kind of large aperture foam silicon-redox graphene based electrochemical decorative material and its preparation method and application |
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN113461856A (en) * | 2021-07-02 | 2021-10-01 | 辽宁大学 | Gel material with electrochemical activity and temperature sensitivity and preparation method and application thereof |
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