CN106018519B - The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol - Google Patents
The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol Download PDFInfo
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Abstract
The invention discloses the applications of complex film modified electrode of a kind of ion liquid functionalization and preparation method thereof and detection chlorophenol.Utilize the special dissolubility of ionic liquid and high electric conductivity, ion liquid functionalization graphene-gold nano grain compound made from epoxy addition is carried out to graphene oxide-gold nano grain compound as amino functional ionic liquid, corresponding complex film modified electrode is prepared for using drop-coating.Gained modified electrode surface of the invention has the characteristics that effective area is big, active site is more, good dispersion, the synergistic effect that ionic liquid, graphene and gold nano grain have been played in terms of improving Direct Electrochemistry and electrocatalysis characteristic, improves the electric conductivity and catalytic performance of modified electrode.Chlorophenol sensor of the gained based on the complex film modified electrode has many advantages, such as that detection limit is low, detection range is wide, response quickly.
Description
Technical field:
The present invention relates to complex film modified electrodes of a kind of ion liquid functionalization and its preparation method and application；Refer specifically to base
In the preparation of ion liquid functionalization graphene-gold nanoparticle composite film modified glassy carbon electrode and Electrochemical Detection application, belong to
In environment protection field.
Background technique:
Chlorophenols compound content in water body is very low, but in chlorine atom on P electronics and phenyl ring pi-electron can be formed it is stable
π-conjugated systems, most of chlorophenol all has very big toxicity, and can be accumulated in biosphere by food chain, is difficult biodegrade,
It is persistence organic pollutant in environment with " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and genetoxic
The Typical Representative of (Persistent Organic Pollutants, POPs).Chlorophenols compound content in water environment is very
Low, there are great difficulties for analysis detection.Currently used detection method mainly has spectrophotometry, fluorescence method, a HPLC, GC-MS,
LC-MS, LC-MS/MS and enzyme-linked immunosorbent assay, although these methods have reliable sensitivity and lower detection limit,
Expensive equipment, the application that sample pretreatment is complicated, operation time-consuming is many and diverse, is unable to the disadvantages of on-site test limits them significantly
[Banimuslem H,Hassan A,Basova T,Gulmez A D,Tuncel S,Durmus M,Gurek A G,Ahsen
V.Copper phthalocyanine/single walled carbon nanotubes hybrid thin films for
pentachlorophenol detection.Sensor Actuat.B 2014,190,990-998.].Electrochemical sensing method because
Its analyze that speed is fast, instrument is simple, easy to operate, low in cost, high sensitivity, selectivity are good and can real-time detection etc. it is excellent
Gesture is applied in the context of detection of chlorophenols compound, is such as based on ZnSe-CTAB/GCE, HRP/Au/GCE, NNH-
The detection of the electrochemical sensor parachlorphenol of MWCNTs/GCE, CD/GRs/CPE composite modified electrode.But that reports at present is such
Electrochemical sensor exist mostly as construct it is complicated, need medium or probe, need " Ping-Pong " of biological enzyme be catalyzed and
The defects of parachlorphenol catalysis oxidation ability is poor is highly detrimental to their practical application and extensive development.Therefore, searching has
The novel electrode decorative material of high electrocatalysis characteristic, developing still has very big challenge for detecting the electrochemical sensor of chlorophenol.
Graphene (Grpahene, GR) be it is closely regularly arranged by single layer of carbon atom, carbon atom is with sp2Hydridization is mutually bonded
Six-membered carbon ring is formed, the lamella (see Fig. 2) with cellular two-dimension plane structure is then extended to form, is to send out in the world at present
Existing most thin carbon material.GR is with the special physics such as at low cost, large specific surface area, thermal stability height, good conductivity, chemistry
And mechanical performance, it has obtained answering extensively in fields such as nanoelectronic, sensor, battery, supercapacitor and energy storage in recent years
With [Gao Z, Wang J, Li Z, Yang W, Wang B, Hou M, He Y, Liu Q, Mann T, Yang P, Zhang M, Liu
L.Graphene Nanosheet/Ni2+/Al3+Layered Double-Hydroxide Composite as a Novel
Electrode for a Supercapacitor.Chem.Mater.2011,23,3509-3516.].Wherein repaired as electrode
Exterior material, due to good electric conductivity and big surface area, the use of GR nanometer sheet not only increases modified electrode to substrate point
The capture ability of son, and its electron transmission is promoted, show excellent electrocatalysis characteristic.It is based on as researcher has used
The electrochemical sensing method of GR modified electrode has detected phosphoric acid ester insecticide, chlorpromazine and 4- in environment with sensitivity
The environmental contaminants such as amino-phenol, catechol, resorcinol and hydroquinone [Meng X, Yin H, Xu M, Ai S, Zhu
J.Electrochemical determination of nonylphenol based on ionic liquid-
functionalized graphene nanosheet modified glassy carbon electrode and its
interaction with DNA.J.Solid State Electrochem.2012,16:2837–2843.].Currently, GR is logical
Often prepared by electronation graphene oxide (GO), but GR is easy to that Severe aggregation occurs in chemical reduction procedure, and
The internal performance that cannot really reflect GR nanometers of monolithics hinders its electron transmission as electrode modified material when significantly
Energy.In order to solve this problem, functional nano-composites first usually are prepared by substrate of monoatomic layer GO nanometer sheet, then carry out
In-situ reducing GO, prepares the GR nano-complex of reduction form, to make GR reach the dispersion of molecular level in composite membrane, most
Limits play the synergistic effect that each component in nano composite membrane improves electron transmission.
Gold nanoparticle (AuNPs) also has good electric conductivity other than with skin effect and quantum size effect
And biocompatibility, can reduce greatly electron donor between receptor at a distance from, improve electronics in interelectrode transmission rate, in electrification
Learning sensory field has important application.But AuNPs generally also will appear agglomeration, drastically influences it and further applies.
Therefore, compound of the preparation based on AuNPs is the important thinking for solving the problems, such as this.
Amino functional ionic liquid is not only a kind of high conductivity, the green solvent with special solubility property, and
Ring-opening reaction can occur with a large amount of epoxide ring in the surface GO for its functional amino, and the composite material table based on GO/GR is arrived in modification
Face.Due to special dissolubility, a large amount of charge and high electric conductivity, the introducing of ionic liquid can greatly improve GO/GR
Dispersibility, stability and the electric conductivity of sill.Currently, using amino functional ionic liquid to GO-AuNPs composite material into
Row epoxy ring opening reaction prepares ion liquid functionalization graphene-gold nano grain compound (IL-GR-AuNPs), and is based on
The research of the complexes membrane modified electrode and its parachlorphenol context of detection has not been reported.The present invention will use electrostatic assembly and be total to
Valence modifies method and prepares IL-GR-AuNPs, prepares corresponding modified electrode and is used for the detection of parachlorphenol.
IL-GR-AuNPs is prepared using electrostatic assembly and covalent modification method, GR nanometer sheet can not only be made successfully to wrap AuNPs
The problem of covering, GR nanometer sheet and AuNPs is effectively inhibited to assemble, improves the specific surface area and electric conductivity of composite material, Er Qietong
Cross the covalent modification of IL, the electric conductivity, dispersibility and stability of compound can also be further increased, give full play to IL, GR and
Advantage of the AuNPs in terms of electrode modification compensates for defect when they are used alone.IL-GR-AuNPs compound is used for
Modified glassy carbon electrode, the nano composite membrane can provide more active sites, higher electric conductivity and good dispersibility, fill
The synergistic effect of three kinds of components is waved in distribution, to improve Direct Electrochemistry and electrocatalysis of the tested substance on modified electrode
Can, it is of great significance to novel high-sensitivity electrochemical detection method is established.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
The kind complex film modified electrode of ion liquid functionalization；I.e. by amino functional ionic liquid to graphene oxide-gold nano grain
Compound carries out IL-GR-AuNPs compound made from epoxy addition, and prepares corresponding modified electrode with the compound.
A kind of complex film modified electrode of ion liquid functionalization provided by the present invention, it is characterised in that the ionic liquid
The complex film modified electrode of functionalization is by glass-carbon electrode as basal electrode, and ion liquid functionalization composite membrane is as electrode modification material
Material composition；The ion liquid functionalization composite membrane is by amino functional ionic liquid to graphene oxide-gold nano grain
Compound carries out ion liquid functionalization graphene-gold nano grain compound made from epoxy addition；The glass-carbon electrode note
For GCE；The graphene oxide is denoted as GO, and the graphene is denoted as GR, and the gold nano grain is denoted as AuNPs；The ion
Liquid is 1- methyl -3- aminopropyl imidazoles hydrobromate, is denoted as IL, structural formula is as follows:
The graphene oxide is denoted as GO, and the graphene is denoted as GR, and the ionic liquid is 1- butyl -3- aminopropyl miaow
Four Chlorine borate of azoles, is denoted as IL, and structural formula is as follows:
It is special the second object of the present invention is to provide a kind of preparation method of complex film modified electrode of ion liquid functionalization
Sign be comprising the following specific steps
(a) preparation of AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, is stirred continuously down and is slowly added to
The sodium citrate solution that 1.5mL mass fraction is 1% continues agitating and heating and boils 15min, and solution becomes aubergine and is cooled to room
Temperature is restored with deionized water to original volume, and AuNPs dispersion liquid is obtained；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasound
Dispersion 2 hours, 3000rpm are centrifuged 10min and remove undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken,
It is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, rear room temperature is sufficiently mixed and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs 10~40mg of GO-AuNPs compound obtained in step (b) to be scattered in 20mL deionized water, thereto
30min is ultrasonically treated after being slowly added to 5~10mg IL and 5~10mg KOH；Dispersion liquid after ultrasound is heated at 80 DEG C and is stirred
Mix reflux for 24 hours, obtained product 8000rmp centrifugation 5min is successively washed 3 times with water and dehydrated alcohol, gained black solid object
Matter is IL-GR-AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid, takes 6~12 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/GCE modification electricity
Pole.
It is characterized in that IL-GR-AuNPs compound described in step (c) is IL multiple with GO-AuNPs under alkaline condition
It closes the epoxide ring in object on GO molecule and occurs what open loop generated；The IL-GR-AuNPs compound is IL covalent modification by GR
The AuNPs composite surface of cladding can be stabilized 2 days, and the then sedimentation completely within 10min of GO-AuNPs hybrid,
The dispersibility and stability of the IL-GR-AuNPs compound are significantly improved.
The three of the object of the invention are to provide a kind of complex film modified electrode of ion liquid functionalization and are preparing electrochemical sensing
Application in terms of device.Specifically, the exactly described complex film modified electrode of ion liquid functionalization the answering in chlorophenol context of detection
With.
More specifically, the chlorophenol is 2,4- Dichlorophenol.
The present invention utilizes the advantages that special solubility property of IL and high electric conductivity, by covalent modification method by amino function
The IL of energyization introduces GR-AuNPs hybrid surface, prepares IL-GR-AuNPs compound；IL-GR- is prepared for using drop-coating
AuNPs/GCE, and constructed the third generation chlorophenol electrochemical sensor based on IL-GR-AuNPs composite membrane.
Compared with prior art, major advantage is: the complex film modified electrode of present invention gained is in terms of electro-catalysis chlorophenol
Played IL, GR and AuNPs synergistic effect: AuNPs improves the specific surface area and electric conductivity of composite membrane, with into inhibiting GR to receive
The aggregation of rice piece；Compound is prepared by substrate of GR nanometer sheet, effectively inhibits the aggregation of AuNPs, the two electrostatic assembly improves
The electro-catalysis and electron transmission efficiency of compound；The covalent modification of IL further enhances the conduction of GR-AuNPs hybrid
Property, dispersibility and stability；IL-GR-AuNPs composite membrane is substantially increased as the bridge between chlorophenol and basal electrode to chlorine
The capture and electro-catalysis ability of phenol.Specifically, the electrochemical catalysis of IL-GR-AuNPs composite membrane parachlorphenol produces unexpected
Technical effect；The electrocatalytic effect of the complex film modified electrode parachlorphenol of gained of the invention, with individual AuNPs or
GR, or compared with the GR-AuNPs compound obtained by chemical reduction method, all tool is significantly improved；Biography of the present invention
Sensor has the characteristics that quick response, Monitoring lower-cut are low, detection range is wide and is suitable for on-site test, method is easy to operate,
Mild condition, preparation cost are low.
Detailed description of the invention:
Fig. 1 for 2 gained IL-GO-AuNPs compound of embodiment 2 institute of electron scanning micrograph (b) and comparative example
Obtain the electron scanning micrograph (a) of GO-AuNPs compound.
Fig. 2 is the optical photograph of 2 gained IL-GO-AuNPs (a) of embodiment and 2 gained GO-AuNPs (b) of comparative example, left figure
The photo of dispersibility when for 0min in water, right figure be 120min after dispersibility photo.
Fig. 3 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 5.0mmol/L [Fe
(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.
Fig. 4 is that the IL-GO-AuNPs in embodiment 2 is repaired with the bare electrode in comparative example 1, the GO-AuNPs in comparative example 2
It adorns electrode and is containing 5.0mmol/L [Fe (CN)6]-3/-4With the impedance diagram in 0.1mol/L KCl solution.
Fig. 5 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 0.2 μm of ol/mL2,4-
In the PBS buffer solution of the pH=8 of Dichlorophenol, sweep speed be 100mV/s when cyclic voltammogram.
Fig. 6 be IL-GO-AuNPs modified electrode obtained in embodiment 2 in the PBS buffer solution of pH=8, sweep speed and be
When 100mV/s, with the DPV curve that 2,4- Dichlorophenol concentration constantly increases, illustration is oxidation peak current and 2,4- Dichlorophenol concentration
Linear relationship.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
(a) preparation of AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, is stirred continuously down and is slowly added to
The sodium citrate solution that 1.5mL mass fraction is 1% continues agitating and heating and boils 15min, and solution becomes aubergine and is cooled to room
Temperature is restored with deionized water to original volume, and AuNPs dispersion liquid is obtained；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasound
Dispersion 2 hours, 3000rpm are centrifuged 10min and remove undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken,
It is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, rear room temperature is sufficiently mixed and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 10mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 5mg IL and 5mg KOH is added；By the dispersion liquid after ultrasound, heating stirring reflux for 24 hours, is obtained at 80 DEG C
The product 8000rmp centrifugation 5min arrived, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-GR-
AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid takes the 8 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/GCE modified electrode.
Embodiment 2:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 20mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
According to the method and condition preparation in step (d) in embodiment 1.
Embodiment 3:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 30mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid takes the 10 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/ GCE modified electrode.
Embodiment 4:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 40mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
According to the method and condition preparation in step (d) in embodiment 3.
Comparative example 1:
Directly use naked GCE.
Comparative example 2:
According to the above-mentioned method for preparing modified electrode, the dispersion that concentration is 1mg/mL is prepared into GO-AuNPs composite material
Liquid takes 8 μ L drop coatings in the glassy carbon electrode surface of milled, obtains GO-AuNPs/GCE after natural drying.
Fig. 1 for 2 gained IL-GR-AuNPs compound of embodiment 2 institute of electron scanning micrograph (b) and comparative example
Obtain the electron scanning micrograph (a) of GO-AuNPs compound.As can be seen that being used as substrate GO from scanning electron microscope (a) figure
Nanometer sheet has a clearly wrinkle striped, the spherical AuNPs of random distribution on its lamella, partial size about 100~
150nm.After IL covalent modification, the boundary of AuNPs obviously becomes weak in IL-GR-AuNPs (figure b) compound, and GR nanometer sheet
Pleated structure almost disappear, the surface of complexes membrane becomes more smooth compared to the GO-AuNPs of non-IL functionalization, this master
If because IL is by occurring ring-opening reaction covalent modification caused by its surface with the epoxide ring on the surface GO.
Fig. 2 is the optical photograph of 2 gained IL-GR-AuNPs (a) of embodiment and 2 gained GO-AuNPs (b) of comparative example.Left figure
The photo of dispersibility when for for 0min in water, right figure be 120min after dispersibility photo.It can be seen from the figure that IL
Product IL-GR-AuNPs after functionalization has good dispersibility in water, also has no sedimentation after 120min；And non-function
The bad dispersibility of the product GO-AuNPs of change in water, this is primarily due to the covalent introducing of IL, can make composite surface band
Charge, simultaneously because the presence of IL special dissolubility and its amino functional group, had IL-GR-AuNPs compound both
Preferable hydrophily, and there is charging property, to have good dispersibility, created condition to prepare modified electrode.
Fig. 3 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 5.0mmol/L [Fe
(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.A curve is the bare electrode in comparative example 1 in [Fe in figure
(CN)6]3-/4-With the cyclic voltammetry curve in 0.1mol/L KCl solution, GO-AuNPs modification electricity in b curve comparison example 2 in figure
The cyclic voltammetry curve of pole, compared to the GCE in comparative example 1, the redox current of the GO-AuNPs/GCE in comparative example 2 increases
It is big, this is because improving electrode interface to [Fe (CN) after AuNPs and the GO electrostatic assembly with high conductivity6]3-/4-'s
Capture ability, and improve its electron transmission efficiency between basal electrode.And c curve is the IL- in embodiment 2 in figure
The cyclic voltammetry curve of GR-AuNPs modified electrode, compared with GCE, GO-AuNPs/GCE in comparative example 1,2, IL-GO-
The redox current of AuNPs/GCE is maximum, this explanation is after covalent modification introduces IL, and IL-GO-AuNPs composite membrane is into one
Step improves the electrocatalysis characteristic of composite membrane.
Fig. 4 is that the IL-GR-AuNPs in embodiment 2 is repaired with the bare electrode in comparative example 1, the GO-AuNPs in comparative example 2
It adorns electrode and is containing 5.0mmol/L [Fe (CN)6]3-/4-With the impedance diagram in 0.1mol/L KCl solution.It can be seen from the figure that
Spectrogram is divided into two parts, and wherein the semicircle under high frequency condition corresponds to effective electronics transfer control process, and half circular diameter represents electricity
Sub- transfer resistance (Ret)；And it is solutes accumulation control process that the linear segment of low-frequency range is corresponding.Electrochemical impedance result is aobvious
Show, the GO-AuNPs/GCE in comparative example 2 is significantly reduced relative to naked GCE, arc radius, illustrates the AuNPs of high conductivity
With the resistance for reducing electron transmission after GO electrostatic assembly.The corresponding IL-GO-AuNPs/GCE of embodiment 2, arc radius is most
It is small, it is almost in straight line, this illustrates that the covalent introducing of IL further enhances the electric conductivity of IL-GO-AuNPs/GCE, thus
Faster electron transport rate is shown, while also illustrating that composite material successfully modifies the surface for having arrived electrode.
Fig. 5 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 0.2 μm of ol/mL2,4-
In the PBS buffer solution of the pH=8 of Dichlorophenol, sweep speed be 100mV/s when cyclic voltammogram.According to figure as can be seen that electrode exists
Contain and there was only oxidation peak in the PBS buffer solution of 2,4- Dichlorophenol, illustrates that the reaction is that irreversible oxidation reaction and electronics pass
Pass process.It can be seen from the figure that (oxidation peak current of the corresponding bare electrode of curve a) is minimum for comparative example 1；In comparative example 2 (b)
The oxidation peak current of corresponding GO-AuNPs/GCE electrode is significantly increased than the peak current of the bare electrode in comparative example 1；Embodiment 2
The redox peak current of IL-GR-AuNPs/GCE electrode after the middle functionalization with IL is maximum, illustrates with GO-AuNPs composite wood
Expect that the electron transport rate of the electrode of modification improves, and the electron transport rate of IL-GR-AuNPs/GCE further increases, and leads
It electrically further enhances, shows best electrocatalysis characteristic.
Fig. 6 be IL-GR-AuNPs modified electrode obtained in embodiment 2 in the PBS buffer solution of pH=8, sweep speed and be
When 100mV/s, with the DPV curve that 2,4- Dichlorophenol concentration constantly increases, illustration is oxidation peak current and 2,4- Dichlorophenol concentration
Linear relationship.With the increase of 2,4- Dichlorophenol concentration, oxidation peak current is gradually increased.When 2,4- Dichlorophenol concentration is 0.01
When~165 μm of ol/L, peak current and 2,4- Dichlorophenol concentration is in a linear relationship, as shown in illustration in Fig. 6, linear equation Ip
(μ A)=- 1.523C (μm ol/L) -0.1169 (R=0.9996), detection are limited to 3.3nM.Its performance is much better than GR-AuNPs/
GCE (detection range is 0.5~48 μm of ol/L, and detection is limited to 50.6nM).It can be seen that IL-GR- obtained in embodiment 2
The features such as 2, the 4- Dichlorophenol electrochemical sensor of AuNPs modified electrode building has the range of linearity wide, and detection limit is low.
Claims (5)
1. a kind of complex film modified electrode of ion liquid functionalization, it is characterised in that the ion liquid functionalization is complex film modified
By glass-carbon electrode as basal electrode, ion liquid functionalization composite membrane forms electrode as electrode modified material；The ion
Liquid functional composite membrane is to carry out epoxy to graphene oxide-gold nano grain compound by amino functional ionic liquid to open
The graphene of ion liquid functionalization made from ring-gold nano grain compound；The glass-carbon electrode is denoted as GCE；The oxidation stone
Black alkene is denoted as GO, and the graphene is denoted as GR, and the gold nano grain is denoted as AuNPs；The ionic liquid is 1- methyl -3- ammonia
Propyl imidazole hydrobromate is denoted as IL, and structural formula is as follows:
The preparation method of the complex film modified electrode of ion liquid functionalization, it is characterised in that comprising the following specific steps
(a) preparation of AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, and is stirred continuously down and is slowly added to 1.5mL mass
Score be 1% sodium citrate solution, continue agitating and heating boil 15min, solution becomes aubergine and is cooled to room temperature, spend from
Sub- water restores to original volume, obtains AuNPs dispersion liquid；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasonic disperse
2 hours, 3000rpm was centrifuged 10min and removes undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken, constantly
The AuNPs dispersion liquid of 10mL is slowly added dropwise under stirring thereto, is sufficiently mixed rear room temperature and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs 10~40mg of GO-AuNPs compound obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 5~10mg IL and 5~10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring is returned at 80 DEG C
For 24 hours, obtained product 8000rmp centrifugation 5min is successively washed 3 times with water and dehydrated alcohol, gained black solid material is stream
For IL-GR-AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the pulpous state liquid that concentration is 1mg/mL with deionized water,
Take 6~12 μ L pulpous state drop-coated on the surface of glass-carbon electrode, naturally dry obtains IL-GR-AuNPs/GCE modified electrode.
2. a kind of preparation method of the complex film modified electrode of ion liquid functionalization according to claim 1, feature exist
The IL-GR-AuNPs compound described in step (c) is IL under alkaline condition and on GO molecule in GO-AuNPs compound
Epoxide ring occurs what open loop generated；The IL-GR-AuNPs compound is IL covalent modification in the AuNPs compound coated by GR
Surface can be stabilized 2 days, and the then sedimentation completely within 10min of GO-AuNPs hybrid, the IL-GR-AuNPs are multiple
The dispersibility and stability for closing object are significantly improved.
3. the complex film modified electrode of a kind of ion liquid functionalization as claimed in claim 1 or 2 is in terms of preparing electrochemical sensor
Application.
4. a kind of application of the complex film modified electrode of ion liquid functionalization according to claim 3, it is characterised in that should
Modified electrode can be used for the detection of chlorophenol.
5. a kind of application of the complex film modified electrode of ion liquid functionalization according to claim 4, it is characterised in that institute
Stating chlorophenol is 2,4- Dichlorophenol.
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