CN104986755A - 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, refer in particular to the preparation method and its usage of a kind of thia Graphene/zinc oxide nanometer composite material, thia Graphene/zinc oxide nanometer composite material prepared by the present invention can be applied to photoelectrochemistry detection field, especially may be used for photoelectrochemistry and detects acetamiprid.
Background technology
In carbon material, graphite is rare is by sp
2the ultra-thin two-dimension web frame that hydbridized carbon atoms is formed, as a kind of carbon material of bi-dimensional cellular crystalline network become by monolayer carbon atom dense arrangement, Graphene has advantages such as conducting electricity very well, the large and electron transfer rate of specific surface area is fast.The elements such as N, B be easily doped to graphite rare in, but as compared to B with N, S doping is very special, S atomic radius is far longer than C atom, and the electronegativity between C (2.55) and S (2.58) differs too little, obvious Charger transfer can not be provided in C-S mixture, therefore, during chemical doping S is rare to graphite, seem quite difficult.But Theoretical Calculation shows, the structure that after doping S atom, meeting distortion graphite is rare, thus promote the performance of Graphene, so it is vital for mixing S atom in graphite is rare.Chinese patent (CN201310080785.3) discloses a kind of method of Graphene being carried out to sulfur doping: provide Graphene, and described Graphene is placed in chemical vapour deposition reaction chamber; Rare gas element is adopted to ventilate and exhaust-gas disposal to described reaction chamber; At 500 ~ 1050 DEG C, pass into sulphur source gas sulfur doping is carried out to described Graphene; In hydrogen and inert gas atmosphere, described reaction chamber is lowered the temperature.The method operation is more loaded down with trivial details, and the chemical Vapor deposition process adopted is high to equipment requirements.
Graphene/metal oxide nano composite material has good dispersiveness and stability, and these characteristics make it be expected to structure for electrochemical sensor and for practical measurement research.ZnO is a kind of semiconductor material with piezoelectricity and photoelectric characteristic, and ZnO energy gap is at normal temperatures 3.37eV, is typical direct band gap semiconductor material with wide forbidden band, has very big using value.In addition, ZnO also has the clear superiority that other semi-conductors a lot of do not possess, as: nontoxic, environment is not destroyed; There is controlled multiple nanostructure, preparation method's variation; Film forming properties is good, can grow under wider temperature window; Good one's own physical property etc.Therefore, ZnO can be used in photoelectric device, has broad application prospects in fields such as ultraviolet detection, optical information storage, acquisition of signal.
Acetamiprid is the new and effective sterilant of chlorination nicotimine class, and it has been widely used in killing many insects.Honeybee can be affected to the sensitivity stimulated and the long-term memory damaging honeybee under acetamiprid lower concentration.In addition, in experiment in vitro, acetamiprid shows genotoxicity to human peripheral blood lymphocytes and cytotoxicity, and indicating acetamiprid can radiation-indued DNA damage.Thus be necessary to study the effective detection method grasping this sterilant, it remains in the environment to reach effective monitoring, reduces the object for beneficial insect and mankind's harm.Some traditional analytical procedures comprise fluorescence (Chinese patent CN201410320883.4), and fluorescent method requires that material used itself will have photoluminescent property; And for example gas phase (GC), liquid phase (LC), high performance liquid phase (HPLC), enzyme-linked immunoassay method has also been used to the detection of acetamiprid.Although these analytical procedures are comparatively sensitive and accurate, their practical application still limits by some factors, and as sample pretreatment step is complicated, expensive equipment, process is consuming time, needs professional etc.
For the deficiencies in the prior art, the present invention with inorganics zinc sulfate for sulphur source and zinc source, while realizing S element doping to Graphene by simple method for calcinating, the load of ZnO at thia graphenic surface can also be realized, prepare thia Graphene/zinc oxide nanometer composite material, further result shows simultaneously, and this matrix material can at room temperature steady in a long-termly exist.This material can be applied to PhotoelectrochemicalTechnique Technique can be quick, sensitive, detect acetamiprid accurately, compared to other detection methods, thia Graphene/zinc oxide nanometer composite material prepared by the present invention has material without the need to having fluorescent characteristic detecting acetamiprid under photoelectrochemistry is combined, sample pretreatment step is simple, and instrument price is cheap, and process is simple, consuming time short, sensitivity advantages of higher.
Summary of the invention
The object of this invention is to provide the preparation method of the single step reaction of a kind of thia Graphene/zinc oxide nanometer composite material, the method can realize the doping of sulphur atom at graphenic surface simply, also achieves the load of Zinc oxide nanoparticle at thia graphenic surface simultaneously.Further, the thia Graphene/zinc oxide nanometer composite material prepared by the method can be used as photoelectrochemistry Sensitive Detection acetamiprid.
The present invention is achieved by the following technical solutions:
A preparation method for 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 mixing solutions, ultrasonic mixing;
Step 3, the graphene oxide of step 2/zinc sulfate mixing solutions is dry, obtain graphene oxide/zinc sulfate solid mixture;
Step 4, the graphene oxide of step 3/zinc sulfate solid mixture proceeded to be full of in the tightness system of rare gas element, tightness system is moved in tubular oven and heat up and calcining at constant temperature, be cooled to room temperature, calcinate taken out, finally obtains 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, rare gas element is argon gas or nitrogen, and tightness system is quartzy sealed tube or stainless steel sealed tube.
In above-mentioned steps 4, Elevated Temperature Conditions is: be warming up to 930 ~ 1000 DEG C with the temperature rise rate of 3 ~ 10 DEG C/min, and constant temperature time is 2 ~ 4h.
Thia Graphene/zinc oxide nanometer composite material prepared by aforesaid method detects acetamiprid for photoelectrochemistry.
Thia Graphene/zinc oxide nanometer composite material, for detecting the using method of acetamiprid, comprises the steps:
Steps A, prepare the DMF dispersion liquid of thia Graphene/zinc oxide nanometer composite material, the DMF dispersant liquid drop getting thia Graphene/zinc oxide nanometer composite material is coated onto ITO conductive glass surface, drying for standby;
Step B, get acetamiprid aptamer (ssDNA) solution be added drop-wise to steps A modified electrode surface, incubated at room, obtains the electrode that acetamiprid is aptamer modified; Drip washing electrode, dried electrode, obtains the ITO electrode ssDNA/S/G/ZnO/ITO that electrochemical aptamer is modified;
Step C, the electrode modified in step B is placed in acetamiprid solution, carries out photoelectrochemical experiments, record experimental data.
In above-mentioned steps A, the DMF dispersion liquid concentration of thia Graphene/zinc oxide nanometer composite material is 1 ~ 2mg/mL, get thia Graphene/zinc oxide nanometer composite material DMF dispersion liquid volume be 10 ~ 20 μ L.
In above-mentioned steps B, acetamiprid aptamer strength of solution of getting is 2 ~ 5 μMs, and volume is 10 ~ 20 μ L.
The invention has the beneficial effects as follows:
(1) while the present invention realizes S element doping to Graphene by simple method for calcinating, the load of ZnO at thia graphenic surface can also be realized, prepare thia Graphene/zinc oxide nanometer composite material.
(2) Graphene specific surface area is large, can realize a large amount of sulphur atom in the doping of graphenic surface and the ZnO load at graphenic surface.
(3) material thia Graphene/zinc oxide that the present invention obtains can be widely used in photoelectrochemistry sensing, photochemical catalysis and battery material field.
(4) material prepared by the present invention can realize detecting the photoelectrochemistry of acetamiprid by simple step, and highly sensitive, required equipment is simple, with low cost, easy handling.
(5) to take aptamer as recognition component detect for the photoelectrochemistry of acetamiprid in the present invention, builds the Photoelectric Detection acetamiprid based on thia Graphene/zinc oxide nanometer composite material.This detection system with modify ITO electrode for working electrode, take photoelectric current as detection signal, by to acetamiprid sample detection, reach the object of the sample containing acetamiprid being carried out to detection by quantitative, and ZnO itself has good electroconductibility, therefore, the load of ZnO can reduce thia Graphene detectability, and Monitoring lower-cut can reach 0.1ng/mL.
Accompanying drawing explanation
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 spectrogram of sample prepared by the embodiment of the present invention 2;
Fig. 3 is the X ray diffracting spectrum of sample prepared by the embodiment of the present invention 1, embodiment 2; The X ray diffracting spectrum of a sample prepared by embodiment 1; The X ray diffracting spectrum of b sample prepared by embodiment 2;
The photocurrent response figure that Fig. 4 is embodiment 1, sample prepared by embodiment 2 detects acetamiprid for photoelectrochemistry.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
In embodiment 2, embodiment 3, graphene oxide used is prepared by the following method:
The preparation of GO adopts the Hummers method improved: under ice-water bath and agitation condition, 1g natural flake graphite is joined the dense H of 50mL
2s
2o
4(98%), in, zero degree is cooled to; Slowly add 0.5g KNO
3with 6g KMnO
4.4h is reacted under control temperature of reaction is no more than the condition of 10 DEG C.Then this system is transferred to 35 DEG C of water bath with thermostatic control stirring reaction 2h, adds 300mL deionized water, under≤80 DEG C of conditions, continue reaction 2h.With excessive 5%H
2o
2reduce remaining KMnO
4, and wash several times with 5%HCl, finally fully wash to solution no longer containing SO with enough deionized waters
4 2-ion (BaCl
2detect without white precipitate).Final product is transferred in 65 DEG C of baking ovens dry, stores for future use.
Embodiment 1
Take 20mg ZnSO
4solid loading is full of in the quartzy sealed tube of Ar, tightness system is put into tubular oven, is warming up to 1000 DEG C of calcinings, and keeps 2h, naturally cool to room temperature with 10 DEG C/min, is taken out by calcinate, finally obtains ZnO monomer.
Sample prepared by the present embodiment is used for the detection of acetamiprid: before tin indium oxide (ITO) conductive glass is modified, ITO conductive glass is positioned over about 30min in the boiling solution of 0.01M NaOH, then it is positioned over respectively ultrasonic irrigation 30min in water and ethanol.2mg ZnO is dispersed in 1mL DMF (DMF), obtains the dispersion liquid that concentration is 2mg/mL.Finally, pipette this ZnO dispersant liquid drop of 20 μ L and be coated onto ITO conductive glass surface, and modify area and be fixed as 0.5cm
2.Dry under finally the ITO conductive glass having modified material being positioned over infrared lamp, obtain the ITO (ZnO/ITO) that ZnO modifies, using this ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL 0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, painting 20 μ L 5 μMs of acetamiprid aptamer (ssDNA) solution are dripped again to the ZnO area territory on this modified electrode, incubated at room, obtain the electrode that acetamiprid is aptamer modified, with Tris-HCl damping fluid and second distillation water wash electrode, nitrogen dries up, obtain the ITO electrode ssDNA/ZnO/ITO that electrochemical aptamer is modified, using this ssDNA/ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL 0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, again this ssDNA/ZnO/ITO electrode being soaked in concentration is respectively 0.1, 0.3, 0.5, 1, 5, 10, 20, 50, 100, in the acetamiprid Tris-HCl buffered soln of 200ng/mL, often soak and once carry out a photoelectrochemical experiments afterwards, record experimental data, drawing standard curve, finally obtaining the Monitoring lower-cut of acetamiprid is 6.7ng/mL.
Embodiment 2
Take 10mg solid oxidation Graphene to be dissolved in 20mL water, be made into 0.5mg/mL graphene oxide water solution.Take 4mg ZnSO
4join in described graphene oxide solution, obtain graphene oxide/ZnSO
4mixing solutions.By graphene oxide/ZnSO
4mixing solutions continual ultrasonic is dry under transferring to 60 DEG C of conditions after 30 minutes, obtains graphene oxide/ZnSO
4solid mixture.By above-mentioned graphene oxide/ZnSO
4solid mixture loading is full of in the quartzy sealed tube of Ar, quartzy sealed tube is put into tubular oven, is warming up to 1000 DEG C with 10 DEG C/min, and keep 2h, naturally cool to room temperature, calcinate is taken out, finally obtains thia Graphene/ZnO nano matrix material S/G/ZnO.
Sample prepared by the present embodiment is used for the detection of acetamiprid: before tin indium oxide (ITO) conductive glass is modified, ITO conductive glass is positioned over about 30min in the boiling solution of 0.01M NaOH, then it is positioned over respectively ultrasonic irrigation 30min in water and ethanol.2mg S/G/ZnO is dispersed in 1mLN, in dinethylformamide (DMF), obtains the dispersion liquid that concentration is 2mg/mL.Finally, pipette this S/G/ZnO dispersant liquid drop of 20 μ L and be coated onto ITO conductive glass surface, and modify area and be fixed as 0.5cm
2.Dry under finally the ITO conductive glass having modified material being positioned over infrared lamp, obtain the ITO (S/G/ZnO/ITO) that S/G/ZnO modifies, using this S/G/ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, painting 20 μ L 5 μMs of acetamiprid aptamer (ssDNA) solution are dripped again to the S/G/ZnO region on this modified electrode, incubated at room, obtain the electrode that acetamiprid is aptamer modified, with Tris-HCl damping fluid and second distillation water wash electrode, nitrogen dries up, obtain the ITO electrode ssDNA/S/G/ZnO/ITO that electrochemical aptamer is modified, using this ssDNA/S/G/ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, again this ssDNA/S/G/ZnO/ITO electrode being soaked in concentration is respectively 0.1, 0.3, 0.5, 1, 5, 10, 20, 50, 100, in the acetamiprid Tris-HCl buffered soln of 200ng/mL, often soak and once carry out a photoelectrochemical experiments, record experimental data, drawing standard curve, finally obtaining the Monitoring lower-cut of acetamiprid is 0.1ng/mL.
Embodiment 3
Take 40mg solid oxidation Graphene to be dissolved in 20mL water, be made into 2mg/mL graphene oxide water solution.Take 80mg ZnSO
4join in described graphene oxide solution, obtain graphene oxide/ZnSO
4mixing solutions.By graphene oxide/ZnSO
4mixing solutions continual ultrasonic is dry under transferring to 60 DEG C of conditions after 30 minutes, obtains graphene oxide/ZnSO
4solid mixture.By above-mentioned graphene oxide/ZnSO
4solid mixture loading is full of N
2stainless steel sealed tube in, stainless steel sealed tube is put into tubular oven, is warming up to 930 DEG C with 3 DEG C/min, and keeps 4h, naturally cool to room temperature, by calcinate take out, finally obtain thia Graphene/ZnO nano matrix material S/G/ZnO.
Sample prepared by the present embodiment is used for the detection of acetamiprid: before tin indium oxide (ITO) conductive glass is modified, ITO conductive glass is positioned over about 30min in the boiling solution of 0.01M NaOH, then it is positioned over respectively ultrasonic irrigation 30min in water and ethanol.2mg S/G/ZnO is dispersed in 1mL DMF (DMF), obtains the dispersion liquid that concentration is 1mg/mL.Finally, pipette this S/G/ZnO dispersant liquid drop of 10 μ L and be coated onto ITO conductive glass surface, and modify area and be fixed as 0.5cm
2.Dry under finally the ITO conductive glass having modified material being positioned over infrared lamp, obtain the ITO (S/G/ZnO/ITO) that S/G/ZnO modifies, using this S/G/ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, painting 10 μ L 2 μMs of acetamiprid aptamer (ssDNA) solution are dripped again to the S/G/ZnO region on this modified electrode, incubated at room, obtain the electrode that acetamiprid is aptamer modified, with Tris-HCl damping fluid and second distillation water wash electrode, nitrogen dries up, obtain the ITO electrode ssDNA/S/G/ZnO/ITO that electrochemical aptamer is modified, using this ssDNA/S/G/ZnO/ITO electrode as working electrode, Ag/AgCl is as reference electrode, platinum filament is as to electrode, be placed in 5mL0.1M PBS (pH 7.4) damping fluid, scan light electrochemistry, record data, after redistilled water clean dry, again this ssDNA/S/G/ZnO/ITO electrode being soaked in concentration is respectively 0.1, 0.3, 0.5, 1, 5, 10, 20, 50, 100, in the acetamiprid Tris-HCl buffered soln of 200ng/mL, often soak and once carry out a photoelectrochemical experiments, record experimental data, drawing standard curve, the Monitoring lower-cut finally obtained is 0.3ng/mL.
The transmission electron microscope picture of Fig. 1 sample prepared by the embodiment of the present invention 2, can see that the ZnO particle of 10nm ~ 40nm is distributed in thia graphenic surface clearly.
The EDS energy spectrogram of sample prepared by Fig. 2 embodiment of the present invention 2, can be able to see spectrogram from EDS, containing S, C, O, Zn tetra-kinds of elements in matrix material, and only containing above-mentioned four kinds of elements.
The X ray diffracting spectrum of a sample prepared by embodiment 1 in Fig. 3; The X ray diffracting spectrum of b sample prepared by embodiment 2; 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 occurred the characteristic peak of Graphene near 2 θ=26 ゜.
Above-mentioned three kinds characterize the successful preparation that S/G/ZnO nano composite material is described.
Fig. 4 is that embodiment 2 detects the photocurrent response figure of acetamiprid for photoelectrochemistry, and curve a is the photocurrent response of ITO electrode S/G/ZnO/ITO in 5mL0.1M PBS (pH 7.4) damping fluid that S/G/ZnO modifies, and can find out, photoelectric current is larger; Curve b is that S/G/ZnO/ITO drips the photocurrent response of modified electrode ssDNA/S/G/ZnO/ITO in 5mL0.1M PBS (pH 7.4) damping fluid after being coated with 20 μ L, 5 μMs of acetamiprid aptamer (ssDNA) solution, can find out, photoelectric current obviously diminishes, this is because after ssDNA modifies electrode surface, with thia Graphene generation bonding, thus reduce electron transport rate, reduce photoelectric current; Curve c is after ssDNA/S/G/ZnO/ITO soaks in the acetamiprid solution of 10ng/mL, photocurrent response in 5mL 0.1M PBS (pH 7.4) damping fluid, can find out, photoelectric current is obvious again modifies the enhancing of the photoelectric current after electrode surface than ssDNA, this is because acetamiprid is combined more firm than the bonding of ssDNA and thia Graphene with ssDNA, result in ssDNA to come off from thia graphenic surface, thia Graphene electron transport rate increases.And ZnO itself has good electroconductibility, therefore, the load of ZnO can reduce thia Graphene detectability.
Foregoing is only the preferred embodiments of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; corresponding flexible or amendment can be carried out very easily; certainly; these amendments made according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (9)
1. a preparation method for thia Graphene/zinc oxide nanometer composite material, is characterized in that, comprise 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 solutions, ultrasonic mixing;
Step 3, the graphene oxide of step 2/zinc sulfate mixing solutions is dry, obtain graphene oxide/zinc sulfate solid mixture;
Step 4, the graphene oxide of step 3/zinc sulfate solid mixture proceeded to be full of in the tightness system of rare gas element, tightness system is moved in tubular oven and heat up and calcining at constant temperature, naturally cool to room temperature, calcinate is taken out, finally obtains thia Graphene/zinc oxide nanometer composite material.
2. the preparation method of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterized in that, graphene oxide, distilled water, zinc sulfate amount ratio are 10 ~ 40mg:20mL:4 ~ 80mg.
3. the preparation method of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 2, it is characterized in that, graphene oxide, distilled water, zinc sulfate amount ratio are 10mg:20mL:4mg.
4. the preparation method of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, is characterized in that, in step 4, rare gas element is argon gas or nitrogen, and tightness system is quartzy sealed tube or stainless steel sealed tube.
5. the preparation method of a kind of thia Graphene/zinc oxide nanometer composite material according to claim 1, it is characterized in that, in step 4, Elevated Temperature Conditions is: be warming up to 930 ~ 1000 DEG C with the temperature rise rate of 3 ~ 10 DEG C/min, and constant temperature time is 2 ~ 4h.
6. the purposes of thia Graphene/zinc oxide nanometer composite material prepared of method according to claim 1, it is characterized in that, this matrix material is used for photoelectrochemistry and detects acetamiprid.
7. the purposes of thia Graphene/zinc oxide nanometer composite material according to claim 6, it is characterized in that, using method comprises the steps:
Steps A, prepare the DMF dispersion liquid of thia Graphene/zinc oxide nanometer composite material, the DMF dispersant liquid drop getting thia Graphene/zinc oxide nanometer composite material is coated onto ITO conductive glass surface, drying for standby;
Step B, get acetamiprid aptamer ssDNA solution be added drop-wise to steps A modified electrode surface, incubated at room, obtains the electrode that acetamiprid is aptamer modified; Drip washing electrode, dried electrode, obtains the ITO electrode ssDNA/S/G/ZnO/ITO that electrochemical aptamer is modified;
Step C, the electrode modified in step B is placed in acetamiprid solution, carries out photoelectrochemical experiments, record experimental data.
8. the purposes of thia Graphene/zinc oxide nanometer composite material according to claim 7, it is characterized in that, in steps A, the DMF dispersion liquid concentration of thia Graphene/zinc oxide nanometer composite material is 1 ~ 2mg/mL, get thia Graphene/zinc oxide nanometer composite material DMF dispersion liquid volume be 10 ~ 20 μ L.
9. the purposes of thia Graphene/zinc oxide nanometer composite material according to claim 7, is characterized in that, in step B, acetamiprid aptamer strength of solution of getting is 2 ~ 5 μMs, and volume is 10 ~ 20 μ L.
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| CN105720251A (en) * | 2015-12-20 | 2016-06-29 | 华南理工大学 | Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material |
| CN106732515A (en) * | 2016-12-12 | 2017-05-31 | 安徽大学 | A kind of preparation method and its usage of the BG/ZnO nano composite materials with p n hetero-junctions |
| CN107655958A (en) * | 2017-09-22 | 2018-02-02 | 山西大学 | Acetamiprid detection method based on ferronickel cyanide complex nano particle for instruction probe |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105445346A (en) * | 2015-11-25 | 2016-03-30 | 江苏大学 | Construction method of photoelectrochemical adaptor sensor based on gold/zinc oxide composite and bisphenol A detection method |
| CN105445346B (en) * | 2015-11-25 | 2018-05-11 | 江苏大学 | A kind of construction method of optical electro-chemistry aptamer sensor based on gold/zinc oxide composite and the detection method to bisphenol-A |
| CN105720251A (en) * | 2015-12-20 | 2016-06-29 | 华南理工大学 | Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material |
| CN105720251B (en) * | 2015-12-20 | 2018-05-15 | 华南理工大学 | A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof |
| CN106732515A (en) * | 2016-12-12 | 2017-05-31 | 安徽大学 | A kind of preparation method and its usage of the BG/ZnO nano composite materials with p n hetero-junctions |
| CN107655958A (en) * | 2017-09-22 | 2018-02-02 | 山西大学 | Acetamiprid detection method based on ferronickel cyanide complex nano particle for instruction probe |
| CN107655958B (en) * | 2017-09-22 | 2019-09-24 | 山西大学 | It is the Acetamiprid detection method for indicating probe based on ferronickel cyanide complex nano particle |
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