CN104986755B - Preparing method and application of sulfur impurity graphene/zinc oxide nanocomposite - Google Patents
Preparing method and application of sulfur impurity graphene/zinc oxide nanocomposite Download PDFInfo
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Abstract
The invention discloses a preparing method and application of sulfur impurity graphene/zinc oxide nanocomposite. The prepared sulfur impurity graphene/zinc oxide nanocomposite can be applied to the field of photoelectrochemistry detection and particularly can be used for photoelectrochemistry detection of acetamiprid. According to the preparing method, graphite oxide and metal sulfate serve as raw materials, and the sulfur impurity graphene/zinc oxide nanocomposite is prepared through a high-temperature calcination method. The sources of raw materials are rich, the preparing technology is simple, and operation is easy. The detection lower limit of the prepared sulfur impurity graphene/zinc oxide nanocomposite for photoelectrochemistry detection of acetamiprid can reach 0.1 ng/mL. The obtained material can also be widely applied to the fields of photoelectrochemistry sensing, photocatalysis and battery materials.
Description
Technical field
The present invention relates to grapheme material field, refers in particular to a kind of preparation of thia Graphene/zinc oxide nanometer composite material
Method and application thereof, thia Graphene/zinc oxide nanometer composite material prepared by the present invention can apply to Optical Electro-Chemistry detection
Field, it is particularly possible to detect Acetamiprid for Optical Electro-Chemistry.
Background technology
In material with carbon element, it is by sp that graphite is dilute2The ultra-thin two-dimension web frame that hydbridized carbon atoms are constituted, as one kind by monolayer
Carbon atom dense arrangement into bi-dimensional cellular lattice structure material with carbon element, Graphene have conduct electricity very well, specific surface area it is big and
The advantages of electron transfer rate is fast.The elements such as N, B be easily doped to graphite it is dilute in, but compare with B with N, S doping be very
Particularly, S atom radius is far longer than the electronegativity between C atoms, and C (2.55) and S (2.58) and differs too little, it is impossible in C-
Obvious electric charge transfer is provided in S complex, therefore, chemical doping S to graphite it is dilute in seem extremely difficult.However, theoretical meter
Show, after doping S atom, the dilute structure of graphite can be distorted, so as to lift the performance of Graphene, so, in the dilute middle incorporation of graphite
S atom it is critical that.Chinese patent (CN201310080785.3) discloses a kind of side that sulfur doping is carried out to Graphene
Method：Graphene is provided, the Graphene is placed in chemical vapour deposition reaction chamber；The reaction chamber is entered using noble gases
Row ventilation and pump-down process；Sulphur source gas is passed through at 500～1050 DEG C carries out sulfur doping to the Graphene；In hydrogen and lazy
The reaction chamber is lowered the temperature in property gas atmosphere.The method operation is cumbersome, and the chemical vapour deposition technique pair for being adopted
Equipment requirements are high.
Graphene/metal oxide nano composite material has good dispersibility and stability, and these characteristics have which
Hope the structure for electrochemical sensor and be used for practical measurement research.ZnO is a kind of partly leading with piezoelectricity and photoelectric characteristic
Body material, ZnO energy gaps at normal temperatures are 3.37eV, are typical direct band gap semiconductor material with wide forbidden band, with pole
Big using value.Additionally, ZnO also has the clear superiority that a lot of other quasiconductors do not possess, such as：It is nontoxic, environment is not had
There is destruction；With controllable various nanostructureds, preparation method variation；Filming performance is good, can be in wider temperature window
Lower growth；Good one's own physical property etc..Therefore, ZnO can be used in photoelectric device, visit in ultraviolet detection, optical information storage, signal
The fields such as survey have broad application prospects.
Acetamiprid is the new and effective insecticide of chlorination nicotimine class, and which has been widely used for killing many insects.Pyridine worm
Apiss can be affected under amidine low concentration to the sensitivity for stimulating and the longterm memory for damaging Apiss.In addition, pyridine worm in experiment in vitro
Amidine shows the genotoxicity to human peripheral blood lymphocytes and cytotoxicity, indicates Acetamiprid and can induce DNA damages
Wound.Thus be necessary to study the effective detection method for grasping the insecticide, which remains in the environment to reach effective monitoring, and it is right to reduce
In the purpose that beneficial insect and the mankind endanger.Some traditional analysis methods include fluorescence (Chinese patent CN201410320883.4),
Fluorescence method requires that material itself used will have photoluminescent property；And for example gas phase (GC), liquid phase (LC), efficient liquid phase (HPLC), enzyme
Linked immunoassay method also has been used for the detection of Acetamiprid.Although these analysis methods are more sensitive and accurate, their reality
Border application is still limited by some factors, and such as sample pretreatment step is complicated, expensive equipment, and process takes, and needs professional
Deng.
For the deficiencies in the prior art, the present invention with inorganic matters zinc sulfate as sulphur source and zinc source, by simple calcining side
While method realizes S element dopings to Graphene, additionally it is possible to realize loads of the ZnO in thia graphenic surface, prepare thia
Graphene/zinc oxide nanometer composite material, while further result shows that the composite can be steady in a long-term at room temperature
Exist.The material can apply to PhotoelectrochemicalTechnique Technique can be quick, sensitive, accurately detect Acetamiprid, compared to other inspections
Survey method, thia Graphene/zinc oxide nanometer composite material prepared by the present invention are detected Acetamiprid in the case where combining with Optical Electro-Chemistry
With material need not have fluorescent characteristic, sample pretreatment step is simple, and instrument price is cheap, and process is simple, time-consuming short, sensitive
The advantages of spending high.
The content of the invention
It is an object of the invention to provide a kind of preparation side of the single step reaction of thia Graphene/zinc oxide nanometer composite material
Method, the method can simply realize doping of the sulphur atom in graphenic surface, while also achieve Zinc oxide nanoparticle existing
The load of thia graphenic surface.Further, by the method prepare thia Graphene/zinc oxide nanometer composite material can
As Optical Electro-Chemistry Sensitive Detection Acetamiprid.
The present invention is achieved by the following technical solutions：
A kind of preparation method of thia Graphene/zinc oxide nanometer composite material, comprises the following steps：
Step 1, solid oxidation Graphene is dissolved in distilled water, is made into graphene oxide water solution；
Step 2, zinc sulfate is dissolved in the graphene oxide water solution of step 1, obtains graphene oxide/zinc sulfate and mix
Solution is closed, ultrasound is mixed；
Step 3, the graphene oxide of step 2/zinc sulfate mixed solution is dried, obtains graphene oxide/zinc sulfate solid
Body mixture；
Step 4, the graphene oxide of step 3/zinc sulfate solid mixture is proceeded to into the sealing device full of noble gases
In, sealing device is moved in tubular heater and is heated up and calcining at constant temperature, be cooled to room temperature, calcined product is taken out, final
To thia Graphene/zinc oxide nanometer composite material.
In above-mentioned steps 1, graphene oxide, distilled water, zinc sulfate amount ratio are 10～40mg:20mL:4～80mg.
In such scheme, graphene oxide, distilled water, zinc sulfate amount ratio are 10mg:20mL:4mg.
In above-mentioned steps 4, noble gases are argon or nitrogen, and sealing device is quartzy seal pipe or rustless steel seal pipe.
In above-mentioned steps 4, Elevated Temperature Conditions are：930～1000 DEG C are warming up to the heating rate of 3～10 DEG C/min, constant temperature
Time is 2～4h.
Thia Graphene/zinc oxide nanometer composite material prepared by said method is used for Optical Electro-Chemistry and detects Acetamiprid.
Thia Graphene/zinc oxide nanometer composite material is used for the using method for detecting Acetamiprid, comprises the steps：
Step A, the DMF dispersion liquids for preparing thia Graphene/zinc oxide nanometer composite material, take thia Graphene/oxidation
The DMF dispersant liquid drops of zinc nano composite material are coated onto ITO conductive glass surfaces, drying for standby；
Step B, the modified electrode surface that Acetamiprid aptamer (ssDNA) solution is added drop-wise to step A is taken, room temperature is incubated
Educate, obtain the aptamer modified electrode of Acetamiprid；Drip washing electrode, dried electrode obtain the ITO of electrochemical aptamer modification
Electrode ssDNA/S/G/ZnO/ITO；
Step C, the electrode modified in step B is placed in Acetamiprid solution, carries out photoelectrochemical experiments, record experiment
Data.
In above-mentioned steps A, the DMF dispersion liquid concentrations of thia Graphene/zinc oxide nanometer composite material are 1～2mg/mL,
The DMF dispersion liquid volumes of taken thia Graphene/zinc oxide nanometer composite material are 10～20 μ L.
In above-mentioned steps B, taken Acetamiprid aptamer solution concentration is 2～5 μM, and volume is 10～20 μ L.
The invention has the beneficial effects as follows：
(1) while the present invention realizes S element dopings to Graphene by simple method for calcinating, additionally it is possible to realize ZnO
In the load of thia graphenic surface, thia Graphene/zinc oxide nanometer composite material is prepared.
(2) Graphene specific surface area is big, be capable of achieving a large amount of sulphur atoms graphenic surface doping and ZnO in Graphene table
The load in face.
(3) the material thia Graphene/Zinc Oxide obtained by the present invention can be widely applied to Optical Electro-Chemistry sensing, photocatalysis
And battery material field.
(4) by simple step, the material prepared by the present invention can realize that the Optical Electro-Chemistry to Acetamiprid is detected, spirit
Sensitivity is high, and equipment needed thereby is simple, with low cost, it is easy to operate.
(5) present invention detects that by the Optical Electro-Chemistry that recognition component is used for Acetamiprid of aptamer structure is based on thia
The Photoelectric Detection Acetamiprid of Graphene/zinc oxide nanometer composite material.The detection system is electric as work with the ITO electrode modified
Pole, with photoelectric current as detection signal, by Acetamiprid sample detection, having reached carries out detection by quantitative to the sample containing Acetamiprid
Purpose, and ZnO itself have good electric conductivity, therefore, the load of ZnO can reduce thia Graphene test limit, under detection
Limit can reach 0.1ng/mL.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of sample prepared by the embodiment of the present invention 2；
Fig. 2 is the EDS energy spectrum diagrams of sample prepared by the embodiment of the present invention 2；
Fig. 3 is the embodiment of the present invention 1, the X ray diffracting spectrum of sample prepared by embodiment 2；A is prepared by embodiment 1
The X ray diffracting spectrum of sample；X ray diffracting spectrums of the b for sample prepared by embodiment 2；
Fig. 4 is that the sample prepared by embodiment 1, embodiment 2 is used for the photocurrent response figure that Optical Electro-Chemistry detects Acetamiprid.
Specific embodiment
With reference to specific embodiment, the invention will be further described：
In embodiment 2, embodiment 3, graphene oxide used is prepared via a method which：
The preparation of GO adopts improved Hummers methods：Under ice-water bath with stirring condition, 1g natural flake graphites are added
To the dense H of 50mL2S2O4(98%), in, it is cooled to zero degree；It is slowly added to 0.5g KNO3With 6g KMnO4.In controlling reaction temperature not
4h is reacted under conditions of more than 10 DEG C.Then the system is transferred to into 35 DEG C of water bath with thermostatic control stirring reactions 2h, add 300mL go from
Sub- water, continues reaction 2h under the conditions of≤80 DEG C.With excessive 5%H2O2Reduce remaining KMnO4If, and washed with 5%HCl
Dry time, finally fully washed to solution with enough deionized waters and no longer contain SO4 2-Ion (BaCl2Detection is without white precipitate).
Final product is transferred in 65 DEG C of baking ovens and is dried, stored for future use.
Embodiment 1
Weigh 20mg ZnSO4Solid loads in the quartzy seal pipe full of Ar, and sealing device is put into tubular heater
In, 1000 DEG C of calcinings are warming up to 10 DEG C/min, and keep 2h, naturally cooled to room temperature, calcined product is taken out, finally give
ZnO monomers.
Sample prepared by the present embodiment is used for into the detection of Acetamiprid：Tin indium oxide (ITO) electro-conductive glass is being repaiied
Before decorations, ITO electro-conductive glass is positioned over into about 30min in the boiling solution of 0.01M NaOH, be then respectively placed in water and
Ultrasonic irrigation 30min in ethanol.2mg ZnO are dispersed in 1mL DMFs (DMF), concentration are obtained for 2mg/
The dispersion liquid of mL.Finally, the 20 μ L ZnO dispersant liquid drops are pipetted and is coated onto ITO conductive glass surfaces, and modify area and be fixed as
0.5cm2.Finally the ITO electro-conductive glass for having modified material is positioned under infrared lamp and is dried, obtain the ITO (ZnO/ of ZnO modifications
ITO), using the ZnO/ITO electrodes as working electrode, Ag/AgCl is placed in 5mL as to electrode as reference electrode, platinum filament
In 0.1M PBS (pH 7.4) buffer, scan Optical Electro-Chemistry, record data, with redistilled water clean dry after, then to this
5 μM of Acetamiprid aptamer (ssDNA) solution of 20 μ L of ZnO area domain drop coating on modified electrode, incubation at room temperature, obtain pyridine worm
The aptamer modified electrode of amidine, with Tris-HCl buffer and second distillation water wash electrode, nitrogen is dried up, and obtains electrification
ITO electrode ssDNA/ZnO/ITO of aptamers modification is learned, using the ssDNA/ZnO/ITO electrodes as working electrode, Ag/AgCl
Used as reference electrode, platinum filament scans Optical Electro-Chemistry, note as to electrode, being placed in 5mL 0.1M PBS (pH 7.4) buffer
Record data, with redistilled water clean dry after, then by the ssDNA/ZnO/ITO electrodes be soaked in respectively concentration for 0.1,0.3,
0.5th, 1,5,10,20,50,100, in the Acetamiprid Tris-HCl buffer solution of 200ng/mL, often soaking once is carried out once afterwards
Photoelectrochemical experiments, record experimental data, draw standard curve, finally give the Monitoring lower-cut to Acetamiprid for 6.7ng/mL.
Embodiment 2
Weigh 10mg solid oxidation Graphenes to be dissolved in 20mL water, be made into 0.5mg/mL graphene oxide water solutions.Claim
Take 4mg ZnSO4It is added in the graphene oxide solution, obtains graphene oxide/ZnSO4Mixed solution.By graphite oxide
Alkene/ZnSO4Mixed solution continual ultrasonic is dried under the conditions of 60 DEG C are transferred to after 30 minutes, obtains graphene oxide/ZnSO4Solid
Mixture.By above-mentioned graphene oxide/ZnSO4Solid mixture loads in the quartzy seal pipe full of Ar, by quartzy seal pipe
Be put in tubular heater, 1000 DEG C are warming up to 10 DEG C/min, and keep 2h, naturally cooled to room temperature, calcined product is taken
Go out, finally give thia Graphene/ZnO nano composite S/G/ZnO.
Sample prepared by the present embodiment is used for into the detection of Acetamiprid：Tin indium oxide (ITO) electro-conductive glass is being repaiied
Before decorations, ITO electro-conductive glass is positioned over into about 30min in the boiling solution of 0.01M NaOH, be then respectively placed in water and
Ultrasonic irrigation 30min in ethanol.2mg S/G/ZnO are dispersed in into 1mLN, in dinethylformamide (DMF), obtaining concentration is
The dispersion liquid of 2mg/mL.Finally, the 20 μ L S/G/ZnO dispersant liquid drops are pipetted and is coated onto ITO conductive glass surfaces, and modify area
It is fixed as 0.5cm2.Finally the ITO electro-conductive glass for having modified material is positioned under infrared lamp and is dried, obtain S/G/ZnO modifications
ITO (S/G/ZnO/ITO), using the S/G/ZnO/ITO electrodes as working electrode, Ag/AgCl makees as reference electrode, platinum filament
It is, to electrode, to be placed in 5mL0.1M PBS (pH 7.4) buffer, scans Optical Electro-Chemistry, record data is washed with second distillation
Only it is after being dried then molten to 20 μ L of S/G/ZnO regions drop coating, the 5 μM of Acetamiprid aptamers (ssDNA) on the modified electrode
Liquid, incubation at room temperature, obtains the aptamer modified electrode of Acetamiprid, with Tris-HCl buffer and second distillation water wash electricity
Pole, nitrogen dry up, and obtain ITO electrode ssDNA/S/G/ZnO/ITO of electrochemical aptamer modification, by the ssDNA/S/G/ZnO/
Used as working electrode, used as reference electrode, platinum filament is used as to electrode, being placed in 5mL0.1M PBS (pH for Ag/AgCl for ITO electrode
7.4), in buffer, scan Optical Electro-Chemistry, record data, with redistilled water clean dry after, then by the ssDNA/S/G/
ZnO/ITO electrodes be soaked in respectively concentration be 0.1,0.3,0.5,1,5,10,20,50,100, the Acetamiprid Tris- of 200ng/mL
In HCl buffer solution, often soak, record experimental data, draw standard curve, it is final to obtain
It is 0.1ng/mL to the Monitoring lower-cut to Acetamiprid.
Embodiment 3
Weigh 40mg solid oxidation Graphenes to be dissolved in 20mL water, be made into 2mg/mL graphene oxide water solutions.Weigh
80mg ZnSO4It is added in the graphene oxide solution, obtains graphene oxide/ZnSO4Mixed solution.By graphite oxide
Alkene/ZnSO4Mixed solution continual ultrasonic is dried under the conditions of 60 DEG C are transferred to after 30 minutes, obtains graphene oxide/ZnSO4Solid
Mixture.By above-mentioned graphene oxide/ZnSO4Solid mixture loads full of N2Rustless steel seal pipe in, rustless steel is sealed
Pipe is put in tubular heater, is warming up to 930 DEG C with 3 DEG C/min, and is kept 4h, naturally cools to room temperature, calcined product is taken
Go out, finally give thia Graphene/ZnO nano composite S/G/ZnO.
Sample prepared by the present embodiment is used for into the detection of Acetamiprid：Tin indium oxide (ITO) electro-conductive glass is being repaiied
Before decorations, ITO electro-conductive glass is positioned over into about 30min in the boiling solution of 0.01M NaOH, be then respectively placed in water and
Ultrasonic irrigation 30min in ethanol.2mg S/G/ZnO are dispersed in 1mL DMFs (DMF), obtaining concentration is
The dispersion liquid of 1mg/mL.Finally, the 10 μ L S/G/ZnO dispersant liquid drops are pipetted and is coated onto ITO conductive glass surfaces, and modify area
It is fixed as 0.5cm2.Finally the ITO electro-conductive glass for having modified material is positioned under infrared lamp and is dried, obtain S/G/ZnO modifications
ITO (S/G/ZnO/ITO), using the S/G/ZnO/ITO electrodes as working electrode, Ag/AgCl makees as reference electrode, platinum filament
It is, to electrode, to be placed in 5mL0.1M PBS (pH 7.4) buffer, scans Optical Electro-Chemistry, record data is washed with second distillation
Only it is after being dried then molten to 10 μ L of S/G/ZnO regions drop coating, the 2 μM of Acetamiprid aptamers (ssDNA) on the modified electrode
Liquid, incubation at room temperature, obtains the aptamer modified electrode of Acetamiprid, with Tris-HCl buffer and second distillation water wash electricity
Pole, nitrogen dry up, and obtain ITO electrode ssDNA/S/G/ZnO/ITO of electrochemical aptamer modification, by the ssDNA/S/G/ZnO/
Used as working electrode, used as reference electrode, platinum filament is used as to electrode, being placed in 5mL0.1M PBS (pH for Ag/AgCl for ITO electrode
7.4), in buffer, scan Optical Electro-Chemistry, record data, with redistilled water clean dry after, then by the ssDNA/S/G/
ZnO/ITO electrodes be soaked in respectively concentration be 0.1,0.3,0.5,1,5,10,20,50,100, the Acetamiprid Tris- of 200ng/mL
In HCl buffer solution, often soak, record experimental data, draw standard curve, it is final to obtain
The Monitoring lower-cut for arriving is 0.3ng/mL.
Fig. 1 is the transmission electron microscope picture of sample prepared by the embodiment of the present invention 2, is clear that 10nm～40nm's
ZnO particle is distributed in thia graphenic surface.
The EDS energy spectrum diagrams of sample prepared by Fig. 2 embodiment of the present invention 2, can see from EDS energy spectrum diagrams, composite
In contain tetra- kinds of elements of S, C, O, Zn, and only contain above-mentioned four kinds of elements.
X ray diffracting spectrums of a for sample prepared by embodiment 1 in Fig. 3；X-rays of the b for sample prepared by embodiment 2
Diffracting spectrum；Find out from the contrast of collection of illustrative plates, from ZnO to S/G/ZnO, do not change the crystal formation of ZnO, and occur in that graphite
Characteristic peak of the alkene near 2 θ=26 ゜.
The above-mentioned three kinds successful preparations for characterizing explanation S/G/ZnO nano composite materials.
Fig. 4 is the photocurrent response figure that embodiment 2 is used for that Optical Electro-Chemistry to detect Acetamiprid, and curve a is S/G/ZnO modifications
Photocurrent response of ITO electrode S/G/ZnO/ITO in 5mL0.1M PBS (pH 7.4) buffer, it can be seen that photoelectric current compared with
Greatly；Curve b is spotted with the modified electrode after 20 μ L, 5 μM of Acetamiprid aptamer (ssDNA) solution for S/G/ZnO/ITO
Photocurrent responses of the ssDNA/S/G/ZnO/ITO in 5mL0.1M PBS (pH 7.4) buffer, it can be seen that photoelectricity lumen
It is aobvious to diminish, this is because ssDNA is modified to after electrode surface, it is bonded with thia Graphene, so as to reduce electron transmission
Speed, reduces photoelectric current；After curve c is soaked in the Acetamiprid solution of 10ng/mL for ssDNA/S/G/ZnO/ITO, in 5mL
Photocurrent response in 0.1M PBS (pH 7.4) buffer, it can be seen that photoelectric current is again substantially than ssDNA modifications to electrode table
Photoelectric current behind face strengthens, this is because Acetamiprid combined with ssDNA it is more firm with being bonded for thia Graphene than ssDNA,
Result in ssDNA to come off from thia graphenic surface, the increase of thia Graphene electron transport rate.And ZnO itself has very well
Electric conductivity, therefore, the load of ZnO can reduce thia Graphene test limit.
The above is only the preferred embodiments of the present invention, is not intended to limit embodiment of the present invention, and this area is general
Logical technical staff central scope of the invention and spirit, can very easily carry out corresponding flexible or modification, certainly,
These modifications made according to present invention spirit, should all be included within scope of the present invention.
Claims (8)
1. a kind of purposes of thia Graphene/zinc oxide nanometer composite material, it is characterised in that the thia Graphene/oxidation
The preparation method of zinc nano composite material is comprised the following steps：
Step 1, solid oxidation Graphene is dissolved in water, is made into graphene oxide water solution；
Step 2, zinc sulfate is dissolved in the graphene oxide water solution of step 1, obtains graphene oxide/zinc sulfate mixing molten
Liquid, ultrasound are mixed；
Step 3, the graphene oxide of step 2/zinc sulfate mixed solution is dried, obtains graphene oxide/zinc sulfate solid and mix
Compound；
Step 4, the graphene oxide of step 3/zinc sulfate solid mixture is proceeded in the sealing device full of noble gases, will
Sealing device heats up and calcining at constant temperature in moving into tubular heater, naturally cools to room temperature, calcined product is taken out, finally give
Thia Graphene/zinc oxide nanometer composite material；
Thia Graphene/the zinc oxide nanometer composite material is used for Optical Electro-Chemistry and detects Acetamiprid.
2. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterised in that
Graphene oxide, water, zinc sulfate amount ratio are 10～40mg:20mL:4～80mg.
3. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 2, it is characterised in that
Graphene oxide, water, zinc sulfate amount ratio are 10mg:20mL:4mg.
4. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterised in that
In step 4, noble gases are argon or nitrogen, and sealing device is quartzy seal pipe or rustless steel seal pipe.
5. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterised in that
In step 4, Elevated Temperature Conditions are：930～1000 DEG C are warming up to the heating rate of 3～10 DEG C/min, constant temperature time is 2～4h.
6. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterised in that
Using method comprises the steps：
Step A, the DMF dispersion liquids for preparing thia Graphene/zinc oxide nanometer composite material, take thia Graphene/zinc oxide nano
The DMF dispersant liquid drops of nano composite material are coated onto ITO conductive glass surfaces, drying for standby；
Step B, the modified electrode surface that Acetamiprid aptamer ssDNA solution is added drop-wise to step A is taken, be incubated at room temperature, obtain
The aptamer modified electrode of Acetamiprid；Drip washing electrode, dried electrode obtain the ITO electrode of electrochemical aptamer modification
ssDNA/S/G/ZnO/ITO；
Step C, the electrode modified in step B is placed in Acetamiprid solution, carries out photoelectrochemical experiments, record experiment number
According to.
7. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 6, it is characterised in that
In step A, the DMF dispersion liquid concentrations of thia Graphene/zinc oxide nanometer composite material are 1～2mg/mL, taken thia graphite
The DMF dispersion liquid volumes of alkene/zinc oxide nanometer composite material are 10～20 μ L.
8. the purposes of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 6, it is characterised in that
In step B, taken Acetamiprid aptamer solution concentration is 2～5 μM, and volume is 10～20 μ L.
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