CN107867713A - A kind of ZnO sensing electrode material preparation methods of porous nano pie structure - Google Patents
A kind of ZnO sensing electrode material preparation methods of porous nano pie structure Download PDFInfo
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Abstract
A kind of ZnO sensing electrode material preparation methods of porous nano pie structure, belong to electric sensing detection hydrazine hydrate applied technical field.Under the conditions of magnetic agitation, by methylimidazole(MIM)And zinc acetate(Zn(CH3COO)2)Hybrid reaction, reaction product is obtained, is centrifuged after being washed with water and ethanol, taken solid phase to be calcined after drying, produce the ZnO sensing electrode materials of porous nano pie structure.The sensing electrode material of the present invention is prepared by magnetic agitation method and calcination method, and the raw material environmental protection of use, rich reserves, cost is low, and preparation technology is simple, easily operated control, green suitable for continuous large-scale production, preparation process.
Description
Technical field
The invention belongs to the technical field of electric sensing detection hydrazine hydrate application.
Background technology
To meet the great demand of removable new energy, excellent performance, inexpensive, the environment-friendly and catalytic of safety are developed
The excellent electric sensing electrode material of energy has caused relevant enterprise and the extensive concern of expert.Be currently owned by special physics and
Chemical property, nano material have been widely used in the fields such as chemical sensor, biology sensor.Zinc oxide material is in recent years
It is rapid to occur, compared with most of noble metals, their cheap rich reserves.At the same time, they have the ability to promote electronics
Transfer reaction and offer have good electro-chemical activity.
Recently, it has been related to the report that metal oxide is used for electro-catalysis.Nano-ZnO has hexagonal wurtzite structure
Direct band-gap semicondictor material, its particle reaction speed are 100~1000 times of common ZnO particles, have larger ratio surface
Product, it is considered to be one of high activity electrocatalysis material of great application prospect, received much concern in Electrochemical Detection environment.But receive
Unstability of the glass-carbon electrode body of rice ZnO modifications in the big concentration range detection of hydrazine hydrate, can not in the range of working concentration
Meet the linear relationship of electric current-concentration well, seriously limit its application.Lot of documents is reported, using the side such as nitrogen-doping
Method, which can reduce ZnO, is kinetically reducing reaction energy levels, effectively improves its electro-catalysis efficiency, therefore, in recent years, by nanometer
Material carries out N doping, to improve applications to nanostructures performance, turns into the study hotspot of nano material synthesis and application field
One of.In the art, N doping is not almost come to strengthen electro-catalysis of the porous pie zinc oxide in hydrazine hydrate detection
The case of performance.So its application and its controlledly synthesis in sensor electrode is difficult urgently to be resolved hurrily.
The content of the invention
Existing background technology and deficiency, the present invention propose a kind of ZnO nano that can be used for detection hydrazine hydrate for more than
The preparation method of material.
The technical scheme is that:Under the conditions of magnetic agitation, by methylimidazole(MIM)And zinc acetate(Zn
(CH3COO)2)Hybrid reaction, reaction product is obtained, is centrifuged after being washed with water and ethanol, take solid phase to be calcined after drying, i.e., much
The ZnO sensing electrode materials of hole nanometer pie structure.
The sensing electrode material of the present invention is prepared by magnetic agitation method and calcination method, the raw material ring of use
Protect, rich reserves, cost is low, and preparation technology is simple, easily operated control, suitable for continuous large-scale production, preparation process green
Environmental protection.
Advantage of the invention is that:
1st, by the acid group of this metal salt institute band of zinc acetate is easily sloughed, it is more easy to obtain required product, therefore present invention process
Using zinc acetate.The present invention is successfully realized the preparation of zinc oxide electrode material.
2nd, using N doping mode, the electrochemical catalysis activity performance of nano zinc oxide material has been expanded.
3rd, the zinc-oxide nano in the present invention can make electrochemical sensor obtain high sensitivity, preferable stability and
Anti-interference etc., the sensing electrode material have a good application prospect in hydrazine hydrate is detected.
Further, the molar ratio of methylimidazole and zinc acetate of the present invention is 6: 5, and the mol ratio can guarantee that
Sheet Zn-ZIF is generated well, and the product morphology and design that are generated using other ratios are then met.
The methylimidazole aqueous solution is added dropwise in zinc acetate aqueous solution, reacted under the conditions of magnetic agitation.The two of the aqueous solution
The zinc acetate of methylimidazole and the aqueous solution is reacted, and complex Zn-ZIF can be generated in theory, in methylimidazole
Molar ratio with zinc acetate can generate the complex of sheet in the case of being 6: 5, this is that other mol ratios do not reach
Effect.The progress that can react fully is added dropwise dropwise, preferably generates sheet Zn-ZIF.
Acetic acid zinc concentration is 0.1 M in the zinc acetate aqueous solution.Because the complex of generation is nano level,
Acetic acid zinc concentration is not suitable for too high.But the too low inadequate subsequent experimental of generated product amount.So 0.1 M is most suitable dense
Degree.
The concentration of the methylimidazole of the methylimidazole aqueous solution is 0.2 M.Because the complex of generation is nanometer
Level, so acetic acid zinc concentration be not suitable for it is too high.But the too low inadequate subsequent experimental of generated product amount.And methylimidazole
Amount with the theoretical reactive material of zinc acetate is 2:1, so 0.2 M is most suitable concentration.
The temperature conditionss of the drying are 60 DEG C.The temperature can well desciccate but will not be led because of temperature is too high
Cause product deterioration.
The calcination condition is:550~750 DEG C are warming up to 1 DEG C per minute of programming rate in oxygen atmosphere, insulation
Normal temperature is naturally cooling to after 2 hours.The setting of the temperature is according to predecessor(Zn-ZIF)Thermogravimetric test result determine.
Brief description of the drawings
Fig. 1 is the small multiplying power SEM figures of zinc oxide electrode material T1 samples made of the present invention.
Fig. 2 is the big multiplying power SEM figures of zinc oxide electrode material T1 samples made of the present invention.
Fig. 3 is the XRD spectra of zinc oxide electrode material T1 samples, T2 samples and T3 samples made of the present invention.
Fig. 4 is the cyclic voltammetry curve figure of zinc oxide electrode material T1 samples, T2 samples and T3 samples made of the present invention.
Fig. 5 is zinc oxide electrode material T1 samples, T2 samples and T3 samples made of the present invention.
Fig. 6 is the stability diagram of zinc oxide electrode material T1 samples, T2 samples and T3 samples made of the present invention.
Fig. 7 is the anti-interference figure of zinc oxide electrode material T1 samples, T2 samples and T3 samples made of the present invention.
Fig. 8 is that electric current-concentration of zinc oxide electrode material T1 samples made of the present invention is accordingly schemed.
Fig. 9 is electric current-concentration linear relationship fitted figure of zinc oxide electrode material T1 samples made of the present invention.
Figure 10 is that electric current-concentration linear relationship of zinc oxide electrode material T1 samples made of the present invention is fitted enlarged drawing.
Embodiment
First, the preparation of zinc oxide sensing electrode material:
Step:The 2-methylimidazole aqueous solution 60mL that concentration is 0.2M is added dropwise to 50mL dropwise, the zinc acetate that concentration is 0.1M
In the aqueous solution, magnetic agitation 24 hours, until system is changed into white depositions completely.
By white depositions deionized water and washes of absolute alcohol three times, drying process in 60 DEG C of baking ovens is placed in afterwards,
Then dry sample is taken out from baking oven, is subsequently placed in tube furnace and calcines, it is final to obtain zinc oxide sample raw material.
2nd, the checking of zinc oxide sensing electrode material:
The present invention has carried out following three groups of parallel tests to calcination condition:
1st, parallel test 1:550 DEG C are warming up to 1 DEG C per minute of programming rate in air atmosphere, then keeps 2 hours,
Room temperature is naturally cooled to, obtains the zinc oxide electrode material T1 samples of porous nanometer structure.
2nd, parallel test 2:650 DEG C are warming up to 1 DEG C per minute of programming rate in air atmosphere, then keeps 2
Hour, room temperature is naturally cooled to, obtains the zinc oxide electrode material T2 samples of porous nanometer structure.
3rd, parallel test 3:750 DEG C are warming up to 1 DEG C per minute of programming rate in air atmosphere, then keeps 2
Hour, room temperature is naturally cooled to, obtains the zinc oxide electrode material T3 samples of porous nanometer structure.
Fig. 1, Fig. 2 are respectively the small multiplying powers of sample T1 and big multiplying power scanning electron microscope (SEM) photograph, and single material is in three-dimensional more as seen from the figure
Hole pie structure.
Fig. 3 is T1 samples, T2 samples and T3 samples(Calcined by different temperatures)XRD spectra.As seen from the figure:Three samples
Standard x RD peaks that the XRD peak types of product are just as and with zinc oxide are consistent.This explanation zinc acetate is by different calcining temperature
Degree, what obtained product was just as, be zinc oxide.
Fig. 4 is the cyclic voltammetry curve figure of T1 samples, T2 samples and T3 samples, as can be observed from Figure, in same concentration
In hydrazine hydrate, the volt-ampere curve of T1 samples is more obvious than two other sample, and this explanation T1 sample has good chemical property.
By glass-carbon electrode(Glass-carbon electrode good conductivity, chemical stability is high, and coefficient of thermal expansion is small, and quality is hard, air-tightness
It is good, it is most important that its potential scope of application is wider than other electrodes in -1~1 V)It is placed in 0.1M NaOH solution, sweeps
Go out the N that stabling current adds 10 μM afterwards2H4.Fig. 7 is the N that T1 samples, T2 samples and T3 samples add 10 μM2H4Electric current afterwards
Stability diagram.Add 10 μM of N2H4The reduction of T1, T2, T3 sample current is respectively 8.7%, 43.1%, 7.4% after 3600s afterwards,
The stability of this explanation T3 sample is preferable.
Fig. 7 is the anti-interference figure of T1, T2, T3 sample.Adding N2H4Afterwards, AA, UA, DA, the KCl of isodose are added,
Its electric current does not fluctuate significantly, this further demonstrates that the anti-interference of T3 samples is good.
3rd, apply:
After the zinc oxide T1 glass-carbon electrodes modified is are connected to electrochemical workstation by Fig. 8, insert containing various concentrations hydrazine hydrate
Phosphate buffer solution PBS (pH=7.2) in, acquisition it is a series of on electric current and the step figure of concentration of hydrazine hydrate.
Fig. 9 is the Linear Fit Chart and its corresponding equation and phase relation in Fig. 8 between electric current and the average of each step
Number.
Figure 10 be linear fit enlarged drawing in Fig. 9 between 0.5-100 μM of concentration of hydrazine hydrate and its corresponding equation to it is related
Coefficient.
In the linear collection of illustrative plates of this standard electrochemical(Fig. 8, Fig. 9)On the basis of, by determining the electricity of the response in hydrazine hydrate solution
Flow valuve, to correspond to the numerical value of corresponding concentration of hydrazine hydrate, and then draw the concentration of hydrazine hydrate in solution.
Claims (7)
1. the ZnO sensing electrode material preparation methods of a kind of porous nano pie structure, it is characterised in that in magnetic agitation condition
Under, by methylimidazole and zinc acetate hybrid reaction, reaction product is obtained, is centrifuged after being washed with water and ethanol, takes solid phase to do
Calcined after dry, produce the ZnO sensing electrode materials of porous nano pie structure.
2. preparation method according to claim 1, it is characterised in that the methylimidazole and zinc acetate feed intake mole
Than for 6: 5.
3. preparation method according to claim 2, it is characterised in that:The methylimidazole aqueous solution is added dropwise in zinc acetate water
In solution, reacted under the conditions of magnetic agitation.
4. preparation method according to claim 3, it is characterised in that:Acetic acid zinc concentration is in the zinc acetate aqueous solution
0.1 M。
5. the preparation method according to claim 3 or 4, it is characterised in that:The dimethyl of the methylimidazole aqueous solution
The concentration of imidazoles is 0.2 M.
6. preparation method according to claim 1, it is characterised in that:The temperature conditionss of the drying are 60 DEG C.
7. preparation method according to claim 1, it is characterised in that:The calcination condition is:With every in oxygen atmosphere
The programming rate of 1 DEG C of minute is warming up to 550~750 DEG C, and insulation is naturally cooling to normal temperature after 2 hours.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108910937A (en) * | 2018-10-18 | 2018-11-30 | 河南师范大学 | A kind of preparation method of ultra-thin spherical self-assembly zinc oxide nanometer sheet |
CN112960686A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | Preparation method of flaky ZnO and application of flaky ZnO in gas chromatography detector |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108910937A (en) * | 2018-10-18 | 2018-11-30 | 河南师范大学 | A kind of preparation method of ultra-thin spherical self-assembly zinc oxide nanometer sheet |
CN112960686A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | Preparation method of flaky ZnO and application of flaky ZnO in gas chromatography detector |
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