CN114740062A - Method for detecting hydrazine by electrochemistry - Google Patents
Method for detecting hydrazine by electrochemistry Download PDFInfo
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000005518 electrochemistry Effects 0.000 title description 3
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 116
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- 239000000243 solution Substances 0.000 claims abstract description 66
- 229920000767 polyaniline Polymers 0.000 claims abstract description 63
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 52
- 239000002114 nanocomposite Substances 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000000835 electrochemical detection Methods 0.000 claims abstract description 10
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 8
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 8
- 239000012086 standard solution Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
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- 229920001661 Chitosan Polymers 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000001514 detection method Methods 0.000 abstract description 14
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 2
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The method for electrochemically detecting hydrazine provided by the disclosure comprises the following steps: s1, preparing a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid; s2, dropwise adding the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid to the surface of a glassy carbon electrode to modify the glassy carbon electrode to form a platinum-polyaniline-reduced graphene oxide glassy carbon electrode; s3, adopting the platinum-polyaniline-reduced graphene oxide glassy carbon electrode as a working electrode of a hydrazine sensor, adopting a phosphate buffer solution as a supporting electrolyte for electrochemical detection, detecting peak current values of hydrazine with different concentrations, and fitting a standard curve by taking the concentration of a hydrazine standard solution as an abscissa and the peak current value as an ordinate; and S4, detecting hydrazine in the solution to be detected according to the standard curve. The method for electrochemically detecting hydrazine provided in the application is adopted to prepare the hydrazine sensor with the detection sensitivity and the detection quantity, wherein the hydrazine sensor is prepared from the platinum-polyaniline-reduced graphene oxide nano composite.
Description
Technical Field
The present disclosure relates to methods for detecting hydrazine using electrochemistry.
Background
Hydrazine hydrate (N)2H4) Has important functions in various fields such as fuel cells, agriculture and the like. However, as a carcinogen, N2H2Is harmful to human health. N is a radical of2H4Volatile and smells more irritating when inhaling N2H4Then, the medicine can cause harm to the lung, the kidney, the liver, the central nervous system, the reproductive system and the like of the organism. Thus, the detection N was developed2H4The analytical method of (2) is highly necessary.
At present, a variety of assays for N have been developed2H4Such as high performance liquid chromatography, spectrophotometry, gas chromatography-mass spectrometry, etc. Meanwhile, electrochemical sensing methods have also received great attention because of their advantages such as good detection performance, simplicity and low cost. Therefore, there is an urgent need to develop a hydrazine hydrate method which is simple, sensitive, highly selective, economical, and suitable for environmental monitoring, food industry, and clinical diagnosis. Therefore, the establishment of an accurate and effective hydrazine hydrate detection method has important application value and practical significance.
Disclosure of Invention
The purpose of the present disclosure is to overcome the deficiencies of the prior art and to provide a method for detecting hydrazine electrochemically.
According to a first aspect of embodiments of the present disclosure, there is provided a method for electrochemically detecting hydrazine, the method comprising the steps of:
s1, preparing a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid;
s2, dropwise adding the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid to the surface of a glassy carbon electrode to modify the glassy carbon electrode to form a platinum-polyaniline-reduced graphene oxide glassy carbon electrode;
s3, adopting the platinum-polyaniline-reduced graphene oxide glassy carbon electrode as a working electrode of a hydrazine sensor, adopting a phosphate buffer solution as a supporting electrolyte for electrochemical detection, detecting peak current values of hydrazine with different concentrations, and fitting a standard curve by taking the concentration of a hydrazine standard solution as an abscissa and the peak current value as an ordinate;
and S4, detecting hydrazine in the solution to be detected according to the standard curve.
In one embodiment, in step S1, the method of preparing a platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid includes:
s11, preparing graphene oxide powder;
s12, preparing polyaniline-graphene oxide composite powder;
s13, preparing platinum-polyaniline-reduced graphene oxide nano composite powder;
s14, adding the platinum-polyaniline-reduced graphene oxide nano composite powder into a chitosan solution for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid.
In one embodiment, in step S11, the method of preparing graphene oxide powder includes:
graphite powder is used as a raw material, and an ultrasonic stripping dispersion method is adopted to synthesize graphene oxide in an ultrasonic bath.
In one embodiment, in step S12, an in-situ chemical polymerization method is used to prepare polyaniline-graphene oxide composite powder.
In one embodiment, in step S12, the method for preparing polyaniline-graphene oxide composite powder by using in-situ chemical polymerization includes:
s121, preparing a graphene oxide solution with the concentration of 0.3-0.7 mg/mL;
s122, taking 15-25mL of the graphene oxide solution prepared in the step S121, dropwise adding 35-45 mu L of aniline solution into the graphene oxide solution, and violently stirring in an ice bath for 25-35 min;
s123, slowly adding 4.3-5.3mL of 0.8-1.2mol/L hydrochloric acid solution into the solution prepared in the step S122, stirring at room temperature for 20-28h, centrifuging, washing with secondary distilled water for several times, and drying in an oven at 50-70 ℃ for 2.5-3.5h to obtain polyaniline-graphene oxide composite powder.
In one embodiment, in step S13, the method of preparing a platinum-polyaniline-reduced graphene oxide nanocomposite powder includes:
s131, preparing polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL;
s132, taking 15-25mL of polyaniline-graphene oxide dispersion liquid prepared in the step S131, adding 3.0-7.0mL of chloroplatinic acid solution with the concentration of 12-18.0mmol/L, and stirring for 7-13 min;
s133, slowly adding 1.5-2.5mL of 1.6-2.2mmol/L sodium borohydride solution into the solution prepared in the step S132, stirring for 80-100min, centrifugally washing for a plurality of times by using ultrapure water, and drying in an oven at the temperature of 50-70 ℃ for 5-7h to prepare the platinum-polyaniline-reduced graphene oxide nano composite powder.
In one embodiment, in step S123, the oxidizing agent includes one or more of ammonium persulfate, hydrogen peroxide, and dichromate.
In one embodiment, in step S14, the adding the platinum-polyaniline-reduced graphene oxide nanocomposite powder into a chitosan solution for ultrasonic dispersion to obtain a platinum-polyaniline-reduced graphene oxide nanocomposite dispersion solution includes
And adding 0.5-1.5g of the platinum-polyaniline-reduced graphene oxide nano-composite powder into 0.5-0.5mL of chitosan solution with the mass fraction of 0.5% for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano-composite dispersion solution.
In one embodiment, in step S2, before the droplet of the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion is applied to the surface of a glassy carbon electrode to modify the glassy carbon electrode, the method further includes:
the surface of the glassy carbon electrode is polished by adopting alumina powder with the grain size of 0.3 mu m, so that the surface of the glassy carbon electrode is changed into a mirror-like structure;
polishing the surface of the glassy carbon electrode again by adopting alumina powder with the grain diameter of 0.05 mu m to ensure that the surface of the glassy carbon electrode is changed into a mirror surface structure;
and repeatedly ultrasonically cleaning the surface of the glassy carbon electrode by using a mixed solution of secondary distilled water and ethanol, wherein the volume ratio of the secondary distilled water to the ethanol is 1: 1.
In one embodiment, in step S3, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and a phosphate buffer solution with a concentration of 0.05-0.15mol/L, pH of 5.5-8.0 is used as a supporting electrolyte for electrochemical detection.
In one embodiment, in step S121, the preparing the graphene oxide solution with a concentration of 0.3-0.7mg/mL includes:
and (3) adding 3-7mg of the graphene oxide powder prepared in the step S11 into 8-12mL of deionized water, and performing ultrasonic dissolution to form a graphene oxide solution with the concentration of 0.3-0.7 mg/mL.
In one embodiment, in step S131, the preparing the polyaniline-graphene oxide dispersion with a mass concentration of 0.5mg/mL includes:
and (3) adding 3-7mg of polyaniline-graphene oxide composite powder prepared in the step S12 into 8-12mL of deionized water, and performing ultrasonic dissolution to form a polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL.
The implementation of the present disclosure includes the following technical effects:
in the method for detecting hydrazine by adopting the electrochemical method, the polyaniline-graphene oxide composite powder is prepared in one step by adopting an in-situ chemical polymerization method, so that the preparation process is simple; in addition, the structure of the platinum-polyaniline-reduced graphene oxide nano composite is beneficial to keeping the surface activity of nano particles, and meanwhile, a larger specific surface area and more reaction sites are provided, so that the detection sensitivity and the detection quantity of the hydrazine sensor manufactured by the platinum-polyaniline-reduced graphene oxide nano composite can be improved.
Drawings
FIG. 1 is a graph of a fitted standard of an embodiment of the present disclosure.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
The method for electrochemically detecting hydrazine provided by the disclosure comprises the following steps:
s1, preparing a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid;
s2, dropwise adding the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid to the surface of a glassy carbon electrode to modify the glassy carbon electrode to form a platinum-polyaniline-reduced graphene oxide glassy carbon electrode;
s3, adopting the platinum-polyaniline-reduced graphene oxide glassy carbon electrode as a working electrode of a hydrazine sensor, adopting a phosphate buffer solution as a supporting electrolyte for electrochemical detection, detecting peak current values of hydrazine with different concentrations, and fitting a standard curve by taking the concentration of a hydrazine standard solution as an abscissa and the peak current value as an ordinate;
and S4, detecting hydrazine in the solution to be detected according to the standard curve.
In one embodiment, in step S1, the method of preparing a platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid includes:
s11, preparing graphene oxide powder;
s12, preparing polyaniline-graphene oxide composite powder;
s13, preparing platinum-polyaniline-reduced graphene oxide nano composite powder;
s14, adding the platinum-polyaniline-reduced graphene oxide nano composite powder into a chitosan solution for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid.
In one embodiment, in step S11, the method of preparing graphene oxide powder includes:
graphite powder is used as a raw material, and an ultrasonic stripping dispersion method is adopted to synthesize graphene oxide in an ultrasonic bath.
In one embodiment, in step S12, an in situ chemical polymerization method is used to prepare the polyaniline-graphene oxide composite powder.
In one embodiment, in step S12, the method for preparing polyaniline-graphene oxide composite powder by using in-situ chemical polymerization includes:
s121, preparing a graphene oxide solution with the concentration of 0.3-0.7 mg/mL;
s122, taking 15-25mL of the graphene oxide solution prepared in the step S121, dropwise adding 35-45 mu L of aniline solution into the graphene oxide solution, and violently stirring in an ice bath for 25-35 min;
s123, slowly adding 4.3-5.3mL of 0.8-1.2mol/L hydrochloric acid solution into the solution prepared in the step S122, wherein the hydrochloric acid solution contains 0.030-0.042g of oxidant, stirring at room temperature for 20-28h, centrifuging, washing with secondary distilled water for several times, and drying in an oven at 50-70 ℃ for 2.5-3.5h to prepare polyaniline-graphene oxide composite powder.
In one embodiment, in step S13, the method of preparing a platinum-polyaniline-reduced graphene oxide nanocomposite powder includes:
s131, preparing polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL;
s132, taking 15-25mL of polyaniline-graphene oxide dispersion liquid prepared in the step S131, adding 3.0-7.0mL of chloroplatinic acid solution with the concentration of 12-18.0mmol/L, and stirring for 7-13 min;
s133, slowly adding 1.5-2.5mL of sodium borohydride solution with the concentration of 1.6-2.2mmol/L into the solution prepared in the step S132, stirring for 80-100min, centrifugally washing with ultrapure water for a plurality of times, and drying in an oven at the temperature of 50-70 ℃ for 5-7h to prepare the platinum-polyaniline-reduced graphene oxide nano composite powder.
In one embodiment, in step S123, the oxidizing agent includes one or any of ammonium persulfate, hydrogen peroxide, and dichromate.
In one embodiment, in step S14, the adding the platinum-polyaniline-reduced graphene oxide nanocomposite powder into a chitosan solution for ultrasonic dispersion to obtain a platinum-polyaniline-reduced graphene oxide nanocomposite dispersion includes
And adding 0.5-1.5g of the platinum-polyaniline-reduced graphene oxide nano-composite powder into 0.5-0.5mL of chitosan solution with the mass fraction of 0.5% for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano-composite dispersion solution.
In one embodiment, in step S2, before the droplet of the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion is applied to the surface of a glassy carbon electrode to modify the glassy carbon electrode, the method further includes:
the surface of the glassy carbon electrode is polished by alumina powder with the grain size of 0.3 mu m, so that the surface of the glassy carbon electrode is changed into a mirror-like structure, and the mirror-like structure can be understood as polishing the surface of the glassy carbon electrode into a mirror-like effect;
the surface of the glassy carbon electrode is polished again by adopting alumina powder with the grain size of 0.05 mu m, so that the surface of the glassy carbon electrode is changed into a mirror surface structure, and the mirror surface structure can be understood as polishing the surface of the glassy carbon electrode into a mirror surface effect;
and repeatedly ultrasonically cleaning the surface of the glassy carbon electrode by using a mixed solution of secondary distilled water and ethanol, wherein the volume ratio of the secondary distilled water to the ethanol is 1: 1.
In one embodiment, in step S3, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and a phosphate buffer solution with a concentration of 0.05-0.15mol/L, pH of 5.5-8.0 is used as a supporting electrolyte for electrochemical detection.
In one embodiment, in step S121, the preparing the graphene oxide solution with a concentration of 0.3-0.7mg/mL includes:
and (3) adding 3-7mg of the graphene oxide powder prepared in the step S11 into 8-12mL of deionized water, and performing ultrasonic dissolution to form a graphene oxide solution with the concentration of 0.3-0.7 mg/mL.
In one embodiment, in step S131, the preparing the polyaniline-graphene oxide dispersion with a mass concentration of 0.5mg/mL includes:
and (3) adding 3-7mg of polyaniline-graphene oxide composite powder prepared in the step S12 into 8-12mL of deionized water, and performing ultrasonic dissolution to form polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL.
In the method for detecting hydrazine by adopting the electrochemical method, the polyaniline-graphene oxide composite powder is prepared in one step by adopting an in-situ chemical polymerization method, so that the preparation process is simple; in addition, the structure of the platinum-polyaniline-reduced graphene oxide nano composite is beneficial to keeping the surface activity of nano particles, and meanwhile, a larger specific surface area and more reaction sites are provided, so that the detection sensitivity and the detection quantity of the hydrazine sensor manufactured by the platinum-polyaniline-reduced graphene oxide nano composite can be improved.
The method of the present disclosure for detecting hydrazine electrochemically will be specifically described below with specific examples.
1. Preparing platinum-polyaniline-reduced graphene oxide nano composite powder:
firstly, graphite powder is used as a raw material, and an ultrasonic stripping dispersion method is adopted to synthesize graphene oxide powder in an ultrasonic bath; then taking 5mg of the graphene oxide powder, ultrasonically dispersing and dissolving the graphene oxide powder by using 10mL of deionized water to form a graphene oxide solution with the concentration of 0.5mg/mL, then taking 20mL of the graphene oxide solution, dropwise adding 40 mu L of aniline solution into the graphene oxide solution, violently stirring the solution in an ice bath for 30min, slowly adding 4.8mL of 1.0mol/L hydrochloric acid solution containing 0.036g of ammonium persulfate, stirring the solution at room temperature for 24h, then carrying out centrifugal treatment, washing the solution with secondary distilled water for three times, and then putting the solution into an oven with the temperature of 60 ℃ to dry the solution for 3h to form polyaniline-graphene oxide composite powder; and finally, taking 5mg of polyaniline-graphene oxide composite powder, performing ultrasonic dispersion and dissolution by using 10mL of deionized water to form polyaniline-graphene oxide dispersion liquid with the concentration of 0.5mg/mL, then taking 20mL of the polyaniline-graphene oxide dispersion liquid, adding 5.0mL of chloroplatinic acid solution with the concentration of 15.0mmol/L into the polyaniline-graphene oxide dispersion liquid, stirring for 10min, firstly slowly adding 2.0mL of sodium borohydride solution with the concentration of 1.9mmol/L into the solution, stirring for 90min, then performing centrifugal washing for a plurality of times by using ultrapure water, putting the solution into an oven with the temperature of 60 ℃, drying for 6h, and preparing the platinum-polyaniline-reduced graphene oxide nano composite powder.
2. Preparing a platinum-polyaniline-reduced graphene oxide glassy carbon electrode:
firstly, grinding the surface of a glassy carbon electrode by using alumina powder with the particle size of 0.3 mu m to ensure that the surface of the glassy carbon electrode is changed into a relatively smooth mirror surface structure, wherein the mirror surface structure can be understood as grinding the surface of the glassy carbon electrode into a similar mirror surface effect, then grinding the surface of the glassy carbon electrode by using the alumina powder with the particle size of 0.05 mu m again to ensure that the surface of the glassy carbon electrode is changed into a very smooth mirror surface structure, and the mirror surface structure can be understood as grinding the surface of the glassy carbon electrode into the mirror surface effect, and then repeatedly ultrasonically cleaning the surface of the glassy carbon electrode by using a mixed solution of redistilled water and ethanol, wherein the volume ratio of the redistilled water to the ethanol is 1: 1; then adding 1mg of the prepared platinum-polyaniline-reduced graphene oxide nanocomposite powder into 1mL of chitosan solution with the mass fraction of 0.5% for ultrasonic dispersion to obtain 1mg/mL of platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid; and finally, dropping 6 mu L of the platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid on the surface of a glassy carbon electrode with a mirror surface structure to modify the glassy carbon electrode, and naturally airing at room temperature for use, wherein the modified electrode is called as a platinum-polyaniline-reduced graphene oxide glassy carbon electrode.
3. Fitting a standard curve:
an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, a platinum-polyaniline-reduced graphene oxide glassy carbon electrode is used as a working electrode of a hydrazine sensor, a phosphate buffer solution with the concentration of 0.05-0.15mol/L, pH of 5.5-8.0 is used as a supporting electrolyte for electrochemical detection, peak current values of hydrazine with different concentrations are detected, the concentration of a hydrazine standard solution is used as a horizontal coordinate, the peak current values are used as a vertical coordinate, and a standard curve is fitted. The fitted standard curve is shown in fig. 1.
4. And detecting the hydrazine hydrate in the solution to be detected according to the standard curve.
The reliability verification of the hydrazine hydrate by adopting electrochemical detection provided by the disclosure comprises the following steps:
1. and (3) verifying linear correlation:
the standard curve obtained in the specific example of the present disclosure as shown in fig. 1 was plotted by origin 8.0 software, and the formula of the fitted standard curve was: y is-1.951 +32.78X, the detection limit is 3.3 μ M, and the linear correlation coefficient R is 0.9978, which meets the requirement of precision, wherein X is the concentration of hydrazine in mol/L, Y is the peak current value of hydrazine in different concentrations in μ a, the detection limit is the minimum concentration or minimum amount of the substance to be detected that can be detected from the sample by a specific analysis method within a given confidence, and the detection limit is 3.3 μmol, which is the minimum concentration or minimum amount of the substance to be detected that can be detected from the sample by a specific analysis method within a given confidence.
Note that, in fig. 1, LOD is 3Sblank/slope, where Sblank is the standard deviation of 10 blanks and the slope of the slope standard curve.
2. And (3) verifying the recovery rate:
table 1 blank spiked recovery: the sample solution to be detected is detected according to the method, and the result is as follows:
and a standard recovery method is adopted to perform a sample test on the platinum-polyaniline-reduced graphene oxide nano glassy carbon electrode. Different concentrations of N2H4Added separately to tap water and the results are shown in table 1. Through experiments, N is found2H4The recovery rate range of (1) is 98.0% -104.0%. This indicates that the substance pair in tap water detects N2H4The influence of (a) is small, and the electrochemical sensor can be applied to N in a sample2H4The detection of (3).
The numerical values in the above experiments are average values measured three times and calculated.
From the data in the above table, N2H4The recovery rate range of (A) is 99.3% -104.0%. This indicates that the substance pair in tap water detects N2H4The effect of (a) is small, and the electrochemical sensor can be applied to N in a sample2H2Detection of (3).
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It will be understood that the present disclosure is not limited to the precise arrangements that have been described above and shown in the drawings, and that various modifications and changes may be made without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.
Claims (10)
1. A method for electrochemically detecting hydrazine is characterized by comprising the following steps:
s1, preparing a platinum-polyaniline-reduced graphene oxide nano-composite dispersion liquid;
s2, dropwise adding the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid to the surface of a glassy carbon electrode to modify the glassy carbon electrode to form a platinum-polyaniline-reduced graphene oxide glassy carbon electrode;
s3, adopting the platinum-polyaniline-reduced graphene oxide glassy carbon electrode as a working electrode of a hydrazine sensor, adopting a phosphate buffer solution as a supporting electrolyte for electrochemical detection, detecting peak current values of hydrazine with different concentrations, and fitting a standard curve by taking the concentration of a hydrazine standard solution as an abscissa and the peak current value as an ordinate;
and S4, detecting hydrazine in the solution to be detected according to the standard curve.
2. The method for electrochemically detecting hydrazine according to claim 1, wherein in step S1, the method for preparing the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion liquid comprises:
s11, preparing graphene oxide powder;
s12, preparing polyaniline-graphene oxide composite powder;
s13, preparing platinum-polyaniline-reduced graphene oxide nano composite powder;
s14, adding the platinum-polyaniline-reduced graphene oxide nano composite powder into a chitosan solution for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano composite dispersion liquid.
3. The method for electrochemically detecting hydrazine according to claim 2, wherein in step S1, the method for preparing graphene oxide powder comprises:
graphite powder is used as a raw material, and an ultrasonic stripping dispersion method is adopted to synthesize graphene oxide in an ultrasonic bath.
4. The method for electrochemically detecting hydrazine according to claim 2, wherein in step S12, polyaniline-graphene oxide composite powder is prepared by in-situ chemical polymerization.
5. The method for electrochemically detecting hydrazine according to claim 4, wherein in step S12, the method for preparing polyaniline-graphene oxide composite powder by in-situ chemical polymerization comprises:
s121, preparing a graphene oxide solution with the concentration of 0.3-0.7 mg/mL;
s122, taking 15-25mL of the graphene oxide solution prepared in the step S121, dropwise adding 35-45 mu L of aniline solution into the graphene oxide solution, and violently stirring in an ice bath for 25-35 min;
s123, slowly adding 4.3-5.3mL of 0.8-1.2mol/L hydrochloric acid solution into the solution prepared in the step S122, stirring at room temperature for 20-28h, centrifuging, washing with secondary distilled water for several times, and drying in an oven at 50-70 ℃ for 2.5-3.5h to obtain polyaniline-graphene oxide composite powder.
6. The method for electrochemically detecting hydrazine according to claim 2, wherein in step S13, the method for preparing platinum-polyaniline-reduced graphene oxide nanocomposite powder comprises:
s131, preparing polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL;
s132, taking 15-25mL of polyaniline-graphene oxide dispersion liquid prepared in the step S131, adding 3.0-7.0mL of chloroplatinic acid solution with the concentration of 12-18.0mmol/L, and stirring for 7-13 min;
s133, slowly adding 1.5-2.5mL of sodium borohydride solution with the concentration of 1.6-2.2mmol/L into the solution prepared in the step S132, stirring for 80-100min, centrifugally washing with ultrapure water for a plurality of times, and drying in an oven at the temperature of 50-70 ℃ for 5-7h to prepare the platinum-polyaniline-reduced graphene oxide nano composite powder.
7. The method for electrochemically detecting hydrazine according to claim 2, wherein in step S14, the step of adding the platinum-polyaniline-reduced graphene oxide nanocomposite powder into the chitosan solution for ultrasonic dispersion to prepare the platinum-polyaniline-reduced graphene oxide nanocomposite dispersion solution comprises:
and adding 0.5-1.5g of the platinum-polyaniline-reduced graphene oxide nano-composite powder into 0.5-0.5mL of chitosan solution with the mass fraction of 0.5% for ultrasonic dispersion to prepare a platinum-polyaniline-reduced graphene oxide nano-composite dispersion solution.
8. A method for detecting hydrazine according to any one of claims 1 to 7, wherein before the step of applying the dispersed Pt-polyaniline-reduced graphene oxide nanocomposite liquid drop to the surface of the glassy carbon electrode to modify the glassy carbon electrode in step S2, the method further comprises:
the surface of the glassy carbon electrode is polished by adopting alumina powder with the grain size of 0.3 mu m, so that the surface of the glassy carbon electrode is changed into a mirror-like structure;
the surface of the glassy carbon electrode is polished again by adopting alumina powder with the grain diameter of 0.05 mu m, so that the surface of the glassy carbon electrode is changed into a mirror surface structure;
repeatedly and ultrasonically cleaning the surface of the glassy carbon electrode by using a mixed solution of secondary distilled water and ethanol, wherein the volume ratio of the secondary distilled water to the ethanol is 1: 1.
9. A method for electrochemical detection of hydrazine as claimed in claim 1, characterized in that in step S3, Ag/AgCl electrode is used as reference electrode, Pt electrode is used as counter electrode, and phosphate buffer solution with concentration of 0.05-0.15mol/L, pH of 5.5-8.0 is used as supporting electrolyte for electrochemical detection.
10. The method for electrochemically detecting hydrazine according to claim 6, wherein the preparing the polyaniline-graphene oxide dispersion liquid with the mass concentration of 0.5mg/mL in step S131 comprises:
and (3) adding 3-7mg of polyaniline-graphene oxide composite powder prepared in the step S12 into 8-12mL of deionized water, and performing ultrasonic dissolution to form polyaniline-graphene oxide dispersion liquid with the concentration of 0.3-0.7 mg/mL.
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