CN107867713B - A kind of ZnO sensing electrode material preparation method of porous nano pie structure - Google Patents
A kind of ZnO sensing electrode material preparation method of porous nano pie structure Download PDFInfo
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Abstract
A kind of ZnO sensing electrode material preparation method of porous nano pie structure, belongs 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, with being centrifuged after water and ethanol washing, the ZnO sensing electrode material to get porous nano pie structure is calcined after taking solid phase dry.Sensing electrode material of the invention is prepared by magnetic agitation method and calcination method, and the raw material environmental protection of use, rich reserves, at low cost, preparation process is simple, easily operated control, is suitable for continuous large-scale production, and preparation process is environmentally protective.
Description
Technical field
The invention belongs to the technical fields of electric sensing detection hydrazine hydrate application.
Background technique
For the great demand for meeting removable new energy, develop have excellent performance, inexpensive, the environmental-friendly and catalytic of safety
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, biosensor.Zinc oxide material is in recent years
Occur rapidly, 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, the report of electro-catalysis is used for about metal oxide.Nano-ZnO has hexagonal wurtzite structure
Direct band-gap semicondictor material, particle reaction speed are 100~1000 times of common ZnO particle, have biggish specific surface
Product, it is considered to be one of high activity electrocatalysis material of great application prospect is concerned in Electrochemical Detection environment.But it receives
Unstability of the glass-carbon electrode body of rice ZnO modification in the big concentration range detection of hydrazine hydrate, cannot within the scope of working concentration
Meet electric current-concentration linear relationship well, seriously limits its application.Lot of documents report, 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, becomes the research hotspot of nano material synthesis and application field
One of.In the art, almost without derived from N doping come enhance porous pie zinc oxide hydrazine hydrate detection in electro-catalysis
The case of performance.So the difficulty of its application and its controlledly synthesis in sensor electrode is urgently to be resolved.
Summary of the invention
A kind of ZnO nano that can be used for detecting hydrazine hydrate is proposed for the above existing background technique and deficiency, the present invention
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, with being centrifuged after water and ethanol washing, calcining is after taking solid phase dry to get more
The ZnO sensing electrode material of hole nanometer pie structure.
Sensing electrode material of the invention is prepared by magnetic agitation method and calcination method, the raw material ring of use
It protects, rich reserves, at low cost, preparation process is simple, easily operated control, is suitable for continuous large-scale production, preparation process green
Environmental protection.
Present invention has an advantage that
1, it since the acid group of this metal salt institute band of zinc acetate is easily sloughed, is easier to obtain required product, therefore the present invention
Technique uses zinc acetate.The present invention is successfully realized the preparation of zinc oxide electrode material.
2, using N doping mode, the electrochemical catalysis activity performance of nano zinc oxide material has been expanded.
3, the present invention in zinc-oxide nano can make electrochemical sensor obtain high sensitivity, preferable stability and
Anti-interference etc., the sensing electrode material have a good application prospect in detection hydrazine hydrate.
Further, the molar ratio of methylimidazole and zinc acetate of the present invention is 6: 5, which can guarantee
Sheet Zn-ZIF is generated well, and other ratios product morphology generated and design is used then to meet.
Methylimidazole aqueous solution is added dropwise in zinc acetate aqueous solution, is reacted under the conditions of magnetic agitation.The two of aqueous solution
The zinc acetate of methylimidazole and aqueous solution is reacted, and complex Zn-ZIF can be generated on theoretical, in methylimidazole
The complex of sheet can be generated in molar ratio with zinc acetate in the case where being 6: 5, this is that other molar ratios are not achieved
Effect.The progress that can react fully is added dropwise dropwise, preferably generation sheet Zn-ZIF.
Acetic acid zinc concentration is 0.1 M in the zinc acetate aqueous solution.Because the complex generated is nanoscale,
Acetic acid zinc concentration is not suitable for excessively high.However the too low inadequate subsequent experimental of product amount generated.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 generated is nanometer
Grade, so acetic acid zinc concentration be not suitable for it is excessively high.However the too low inadequate subsequent experimental of product amount generated.And methylimidazole
Amount with the theoretical reactive material of zinc acetate is 2:1, so 0.2 M is most suitable concentration.
The temperature condition of the drying is 60 DEG C.The temperature can well desciccate but will not be led because of temperature is excessively high
Cause product deterioration.
The calcination condition are as follows: be warming up to 550~750 DEG C in oxygen atmosphere with 1 DEG C of heating rate per minute, heat preservation
Room temperature is naturally cooling to after 2 hours.The setting of the temperature is determined according to the thermogravimetric test result of predecessor (Zn-ZIF).
Detailed description of the invention
Fig. 1 is the small multiplying power SEM figure of zinc oxide electrode material T1 sample made of the present invention.
Fig. 2 is the big multiplying power SEM figure of zinc oxide electrode material T1 sample made of the present invention.
Fig. 3 is the XRD spectra of zinc oxide electrode material T1 sample made of the present invention, T2 sample and T3 sample.
Fig. 4 is the cyclic voltammetry curve figure of zinc oxide electrode material T1 sample made of the present invention, T2 sample and T3 sample.
Fig. 5 is zinc oxide electrode material T1 sample, T2 sample and T3 sample made of the present invention.
Fig. 6 is the stability diagram of zinc oxide electrode material T1 sample made of the present invention, T2 sample and T3 sample.
Fig. 7 is the anti-interference figure of zinc oxide electrode material T1 sample made of the present invention, T2 sample and T3 sample.
Fig. 8 is that electric current-concentration of zinc oxide electrode material T1 sample made of the present invention is accordingly schemed.
Fig. 9 is electric current-concentration linear relationship fitted figure of zinc oxide electrode material T1 sample made of the present invention.
Figure 10 is that electric current-concentration linear relationship of zinc oxide electrode material T1 sample made of the present invention is fitted enlarged drawing.
Specific embodiment
One, 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 vinegar that concentration is 0.1M
In sour zinc aqueous solution, magnetic agitation 24 hours, until system becomes white depositions completely.
Three times by white depositions deionized water and washes of absolute alcohol, be placed in 60 DEG C of baking ovens is dried,
Then dry sample is taken out from baking oven, is subsequently placed in tube furnace and is calcined, it is final to obtain zinc oxide sample raw material.
Two, the verifying of zinc oxide sensing electrode material:
The present invention has carried out following three groups of parallel tests to calcination condition:
1, parallel test 1: being warming up to 550 DEG C in air atmosphere with 1 DEG C of heating rate per minute, then keeps 2
Hour, cooled to room temperature obtains the zinc oxide electrode material T1 sample of porous nanometer structure.
2, parallel test 2: being warming up to 650 DEG C in air atmosphere with 1 DEG C of heating rate per minute, then keeps 2
Hour, cooled to room temperature obtains the zinc oxide electrode material T2 sample of porous nanometer structure.
3, parallel test 3: being warming up to 750 DEG C in air atmosphere with 1 DEG C of heating rate per minute, then keeps 2
Hour, cooled to room temperature obtains the zinc oxide electrode material T3 sample of porous nanometer structure.
Fig. 1, Fig. 2 are respectively the small multiplying power 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 the XRD spectra of T1 sample, T2 sample and T3 sample (calcining by different temperatures).As seen from the figure: three samples
The XRD peak type of product is the same and is consistent with the peak standard x RD of zinc oxide.This illustrates zinc acetate by different calcining temperature
Degree, it is zinc oxide that obtained product, which is the same,.
Fig. 4 is the cyclic voltammetry curve figure of T1 sample, T2 sample and T3 sample, as can be observed from Figure, in same concentration
In hydrazine hydrate, the volt-ampere curve of T1 sample is more obvious than other two sample, this illustrates that 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 the NaOH solution of 0.1M, it sweeps
10 μM of N is added after stabling current out2H4.Fig. 7 is the N that T1 sample, T2 sample and T3 sample are added 10 μM2H4Electric current afterwards
Stability diagram.10 μM of N is added2H4The reduction of T1, T2, T3 sample current is respectively 8.7%, 43.1%, 7.4% after 3600s afterwards,
This illustrates that the stability of T3 sample is preferable.
Fig. 7 is the anti-interference figure of T1, T2, T3 sample.N is being added2H4Afterwards, AA, UA, DA, the KCl of isodose is added,
Its electric current does not fluctuate significantly, this further demonstrates that the anti-interference of T3 sample is good.
Three, it applies:
Fig. 8 is after the zinc oxide T1 glass-carbon electrode modified is connected to electrochemical workstation, and merging contains various concentration water
In the phosphate buffer solution PBS (pH=7.2) for closing hydrazine, a series of step figures about electric current and concentration of hydrazine hydrate of acquisition.
Fig. 9 is Linear Fit Chart between electric current and the mean value of each step and its corresponding equation and phase relation in Fig. 8
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.
On the basis of the linear map of this standard electrochemical (Fig. 8, Fig. 9), pass through the response electricity in measurement hydrazine hydrate solution
Flow valuve to correspond to the numerical value of corresponding concentration of hydrazine hydrate, and then obtains the concentration of hydrazine hydrate in solution.
Claims (2)
1. a kind of ZnO sensing electrode material preparation method of porous nano pie structure, it is characterised in that by methylimidazole water
Solution is added dropwise in zinc acetate aqueous solution, reacts under the conditions of magnetic agitation, and the molar ratio of methylimidazole and zinc acetate is 6
: 5, acetic acid zinc concentration is 0.1 M in the zinc acetate aqueous solution；The methylimidazole of the methylimidazole aqueous solution it is dense
Degree is 0.2 M；Reaction product is obtained, with being centrifuged after water and ethanol washing, is calcined after taking solid phase dry, the calcination condition
Are as follows: 550~750 DEG C are warming up to 1 DEG C of heating rate per minute in oxygen atmosphere, heat preservation is naturally cooling to often after 2 hours
Temperature to get porous nano pie structure ZnO sensing electrode material.
2. preparation method according to claim 1, it is characterised in that: the temperature condition of the drying is 60 DEG C.
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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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