CN113804737B - Polyaniline loaded silver/cuprous oxide multi-element nanocomposite and preparation method of modified electrode - Google Patents
Polyaniline loaded silver/cuprous oxide multi-element nanocomposite and preparation method of modified electrode Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 80
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 49
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000004332 silver Substances 0.000 title claims abstract description 21
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 124
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 60
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012265 solid product Substances 0.000 claims abstract description 26
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims abstract description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000011858 nanopowder Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229940071536 silver acetate Drugs 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- 238000012360 testing method Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 10
- 238000000083 pulse voltammetry Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000000840 electrochemical analysis Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004832 voltammetry Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 80
- 229960003638 dopamine Drugs 0.000 description 40
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 34
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 34
- 229940116269 uric acid Drugs 0.000 description 34
- 238000001514 detection method Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000006872 improvement Effects 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000011943 nanocatalyst Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000000835 electrochemical detection Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- FEINKSYUAFDBNS-UHFFFAOYSA-N dichloromethane;1-methylpyrrolidin-2-one Chemical compound ClCCl.CN1CCCC1=O FEINKSYUAFDBNS-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 210000003722 extracellular fluid Anatomy 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 201000001431 Hyperuricemia Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 230000003187 abdominal effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 230000004144 purine metabolism Effects 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
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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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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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
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
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Abstract
The invention provides a polyaniline-loaded silver/cuprous oxide multi-element nanocomposite and a preparation method of a modified electrode, wherein the preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite comprises the following steps: s1, dispersing aniline monomer in dichloromethane; s2, sequentially adding N-methyl pyrrolidone solution and camphorsulfonic acid under stirring to react at room temperature; s3, adding ammonium persulfate aqueous solution into the reaction solution, standing for reaction, separating dichloromethane at the lower layer, and filtering the residual solution to obtain a solid product; s4, cleaning and drying the product to obtain camphorsulfonic acid doped PANI nano powder; s5, dissolving the PANI nano powder in PBS solution, adding glycol for mixing, and then adding the copper sulfate pentahydrate and the silver acetate solution for fully mixing to obtain PANI nanocomposite precursor solution; s6, dissolving NaOH and glucose in a PBS solution, adding the precursor solution, mixing, heating and reacting, filtering, cleaning and drying the product after the reaction is finished to obtain the PANI nanocomposite powder.
Description
Technical Field
The invention particularly relates to a polyaniline-loaded silver/cuprous oxide multi-element nanocomposite and a preparation method of a modified electrode.
Background
Dopamine (DA) plays an important role in the functions of the human metabolism, central nervous, cardiovascular, hormonal, renal and other systems. Abnormal levels of DA can cause neurological disorders such as schizophrenia, parkinson's disease, and epilepsy. Uric Acid (UA) is a product of purine metabolism in organisms. Abnormal UA levels are associated with a variety of diseases including Lesch-Nyan disease, intestinal, abdominal and hyperuricemia. The concentration of DA in the extracellular fluid of healthy individuals is extremely low (1X 10 -8 ~1×10 -6 M) the concentration of DA in extracellular fluid of Parkinson patients was lower (1X 10) -9 M). The biological important compounds such as DA and UA can be detected with high sensitivity, and the biological important compounds have important significance for pathological, clinical and biological research. Thus, the first and second substrates are bonded together,it is necessary to design a strategy for high sensitivity and selective dopamine detection. Many techniques are currently used for quantitative detection of DA and UA, such as detection methods of fluorescence, electrochemiluminescence, high performance liquid chromatography, capillary electrophoresis, and electrochemical analysis.
The electrochemical analysis method has the advantages of high sensitivity, easy miniaturization, low cost, simple preparation and the like, and becomes a hot spot of current research. However, when detected using conventional electrodes, the oxidation peak potentials of these biomolecules are almost in the same region. This results in an overlap of their voltammetric responses, so that the co-existence of DA and UA cannot be tested directly by conventional bare electrodes.
Disclosure of Invention
The invention provides a polyaniline nanofiber-loaded silver/cuprous oxide nanocomposite (PANI-Cu) 2 OAg) and a preparation method of the modified electrode, and is used for high-sensitivity and selective electrochemical detection of DA and UA. The method effectively solves the problems of simultaneous detection, interference resistance and sensitivity of DA and UA in the detection process of DA and UA.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of polyaniline-loaded silver/cuprous oxide multi-element nanocomposite material comprises the following steps:
s1: adding 0.5mL of aniline monomer into 50mL of dichloromethane solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, stirring at room temperature for a preset time, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared in the step S2, standing for reaction for a preset time, separating the lower dichloromethane layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution by ultrasonic, adding 25ml of ethylene glycol, fully mixing, adding a preset amount of copper sulfate pentahydrate and silver acetate solution, and fully mixing to obtain PANI nanocomposite precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nanocomposite precursor solution, uniformly mixing, heating at 120 ℃ for reaction for a preset time, filtering the product after the reaction by a mixed filter membrane, washing the filtered solid product, and drying to obtain the PANI nanocomposite powder.
As a further improvement, S5 was added specifically 75mg of copper sulfate pentahydrate and 3.77ml of a 47.93mM silver acetate solution.
The invention also provides a preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode, which comprises the following steps:
1): polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
2): adding 2mg of PANI nanocomposite powder prepared by the method and 10 μl of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
3): and (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nanocomposite modified electrode.
As a further improvement, the preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode further comprises the steps of carrying out Cyclic Voltammetry (CV) scanning for 2 hours under the condition of 0.1M PBS (pH 6.8) and potential range of-0.1V-0.9V (vs. SCE), and then carrying out constant potential scanning for 30 minutes under the condition of 0V; after repeating the above operation 3 times, the modified electrode after the treatment was immersed in a 0.1M PBS solution for use.
The invention further provides a polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode prepared by the preparation method, and the test environment is as follows: the PANI nanocomposite modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a pulse voltammetry (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, the pulse width is 50ms, and the DPV test is carried out in a 0.1M PBS solution with pH=6.8.
As a further improvement, the modified electrode was potentiostatic scanned at 0V for 30s prior to each DPV test.
The beneficial effects of the invention are as follows: the electrode modified by the PANI nanocomposite material can realize the simultaneous detection of DA and UA concentrations in DA and UA coexisting solutions; the detection limit of the modified electrode to DA is 0.005 mu M, the detection limit of the modified electrode to UA is 1 mu M, and DA and UA are in PANI-Cu in DPV test 2 The OAg modified electrode has obvious electrochemical response signals and excellent detection sensitivity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of PANI-based series nanocatalysts.
FIG. 2 shows PANI-Cu 2 DPV test pattern of OAg nanocatalyst modified electrode in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA.
FIG. 3 is a graph of DPV test of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) solution containing 200. Mu.M DA.
FIG. 4 is a graph of DPV test of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) solution containing 1mM UA.
FIG. 5 is a PANI-Cu 2 OAg modified electrode DPV test patterns in 0.1M PBS (pH 6.8) solutions containing different concentrations of DA.
FIG. 6 shows DA in PANI-Cu 2 Standard curve for DPV test on OAg modified electrode.
FIG. 7 is a PANI-Cu 2 Schematic of DPV test in 0.1M PBS (pH 6.8) solutions containing various concentrations of UA.
FIG. 8 shows UA in PANI-Cu 2 Standard curve for DPV test on OAg modified electrode.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of a polyaniline-loaded silver/cuprous oxide multi-element nanocomposite, which comprises the following steps:
s1: adding 0.5mL of aniline monomer into 50mL of dichloromethane solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, stirring at room temperature for a preset time, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared in the step S2, standing for reaction for a preset time, separating the lower dichloromethane layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution by ultrasonic, adding 25ml of ethylene glycol, fully mixing, adding a preset amount of copper sulfate pentahydrate and silver acetate solution, and fully mixing to obtain PANI nanocomposite precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nanocomposite precursor solution, uniformly mixing, heating at 120 ℃ for reaction for a preset time, filtering the product after the reaction by a mixed filter membrane, washing the filtered solid product, and drying to obtain the PANI nanocomposite powder.
As a further improvement, S5 was added specifically 75mg of copper sulfate pentahydrate and 3.77ml of a 47.93mM silver acetate solution.
As a further improvement, the stirring time at room temperature in S2 is 20-30min.
As a further improvement, the standing reaction time in S3 is 60-90min.
As a further improvement, the specific steps of S4 are: washing the solid product with distilled water and ethanol in turn, cleaning the filtered product, and naturally airing to obtain camphorsulfonic acid doped PANI nano powder.
As a further improvement, the heating reaction time in S6 is 3-4h; s6, cleaning and drying the solid product, wherein the specific steps are as follows: filtering to obtain a solid product, cleaning the solid product by pure water and ethanol, and naturally airing to obtain the PANI nanocomposite powder.
The embodiment further provides a preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode, which comprises the following steps:
1): polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
2): adding 2mg of PANI nanocomposite powder prepared by the method and 10 μl of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
3): and (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nanocomposite modified electrode.
As a further improvement, the preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode further comprises the steps of carrying out Cyclic Voltammetry (CV) scanning for 2 hours under the condition of 0.1M PBS (pH 6.8) and potential range of-0.1V-0.9V (vs. SCE), and then carrying out constant potential scanning for 30 minutes under the condition of 0V; repeating the operation for 3 times, and immersing the treated modified electrode in 0.1M PBS solution for standby; the prepared catalyst modified electrode is preprocessed to obtain an electrochemical detection signal with good stability and repeatability in the electrochemical test process.
The polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode prepared based on the preparation method has the following testing environment: the PANI nanocomposite modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a pulse voltammetry (DPV) test is carried out, the potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, the pulse width is 50ms, and the DPV test is carried out in a 0.1M PBS solution with pH=6.8. Before each DPV test, the modified electrode is scanned for 30s under the condition of 0V to make the modified electrode material in electrochemical reduction state so as to obtain stable and high-sensitivity electrochemical signal.
Example 1
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
Taking 400mg of camphorsulfonic acid doped PANI powder, dissolving in 5ml of 0.1M PBS solution by ultrasonic, adding 25ml of glycol, stirring and fully mixing by ultrasonic, adding 75mg of cupric sulfate pentahydrate and 3.77ml of 47.93mM silver acetate solution, and fully mixing to obtain the PANI nanocomposite precursor solution. And (3) adding 0.1g of NaOH and 3g of glucose into 5ml of 0.1M PBS solution, stirring or ultrasonically dissolving, adding into the PANI nanocomposite precursor solution, uniformly mixing, transferring to a hydrothermal reaction kettle, and heating at 120 ℃ for 3 hours. After the reaction is finished, filtering the solid product by a mixed filter membrane with the aperture of 0.22 mu m, cleaning the solid product by pure water and ethanol, and naturally airing to obtain a PANI nanocomposite (PANI-Cu) 2 OAg) powder.
The glassy carbon electrode with the diameter of 5mm is polished on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washed by distilled water, ultrasonically washed in absolute ethyl alcohol and distilled water respectively and then dried for standby. 2mg of PANI nanocomposite powder and 10. Mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
The electrochemical test adopts a three-electrode system, wherein a PANI nanocomposite modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Comparative example 1
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
The glassy carbon electrode with the diameter of 5mm is polished on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washed by distilled water, ultrasonically washed in absolute ethyl alcohol and distilled water respectively and then dried for standby. 2mg of PANI nanopowder and 10. Mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
The electrochemical experiment adopts a three-electrode system, wherein a PANI modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Comparative example 2
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
Dissolving 400mg of camphorsulfonic acid doped PANI powder in 5ml of 0.1M PBS solution by ultrasonic, adding 25ml of glycol, stirring, ultrasonic sufficiently mixing, adding 0.15g of copper sulfate pentahydrate, and sufficiently mixing to obtain PANI-Cu 2 O precursor solution. Another 5ml of 0.1M PBS solution is added with 0.1g NaOH and 3g glucose, and the PANI-Cu is added after stirring or ultrasonic dissolution 2 And (3) in the O precursor solution, uniformly mixing, transferring to a hydrothermal reaction kettle, and heating for 3 hours at 120 ℃. After the reaction is finished, filtering the solid product by a mixed system filter membrane with the aperture of 0.22 mu m, cleaning the solid product by pure water and ethanol, and naturally airing to obtain the PANI-Cu 2 O powder.
The glassy carbon electrode with the diameter of 5mm is polished on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washed by distilled water, ultrasonically washed in absolute ethyl alcohol and distilled water respectively and then dried for standby. Will 2mg PANI-Cu 2 O powder and 10. Mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
Electrochemical testing employs a three-electrode system in which PANI-Cu is used 2 The O modified electrode is a working electrode, the graphite electrode is a counter electrode, and the Saturated Calomel Electrode (SCE) is a reference electrode, so as to carry out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Comparative example 3
50mL of methylene chloride was added to the round bottom flask, and 0.5mL of aniline monomer was added to the methylene chloride solution and dispersed uniformly by sonication to form a clear and homogeneous organic phase solution. The resulting organic phase solution was placed on a magnetic stirrer, 50mL of a 0.2mol/L aqueous solution of N-methylpyrrolidone was added to the solution under stirring, 2.323g of camphorsulfonic acid was added thereto, and the mixture was stirred at room temperature for 20 minutes and then allowed to stand. 0.3g of ammonium persulfate is weighed and dissolved in 5mL of water, after the ammonium persulfate solution is completely dissolved, the ammonium persulfate solution is slowly added into the dichloromethane-N-methyl pyrrolidone reaction solution under the standing condition along the bottle wall of a round-bottom flask, after the standing reaction is carried out for 60 minutes, the lower dichloromethane layer is sucked out by a rubber head dropper and is poured into a waste liquid bottle. Filtering the residual solution with a mixed system filter membrane with the aperture of 0.22 mu m to obtain a solid product, washing and cleaning the filtered product with distilled water and ethanol in sequence, and naturally airing to obtain the camphorsulfonic acid doped PANI nano powder.
400mg of camphorsulfonic acid doped PANI powder is taken and dissolved in 5ml of 0.1M PBS solution by ultrasonic, 25ml of glycol is added, and after being fully mixed by stirring ultrasonic, 7.54ml of 47.93mM silver acetate solution is fully mixed to obtain PANI-Ag precursor solution. Another 5ml of 0.1M PBS solution is taken, 0.1g NaOH and 3g glucose are added, the mixture is stirred or dissolved by ultrasonic, and then the mixture is added into the PANI-Ag precursor solution, and after being uniformly mixed, the mixture is transferred to a hydrothermal reaction kettle and heated for 3 hours at 120 ℃. After the reaction is finished, filtering the solid product by using a mixed filter membrane with the aperture of 0.22 mu m, cleaning the solid product by using pure water and ethanol, and naturally airing the solid product to obtain PANI-Ag powder.
The glassy carbon electrode with the diameter of 5mm is polished on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washed by distilled water, ultrasonically washed in absolute ethyl alcohol and distilled water respectively and then dried for standby. 2mg of PANI-Ag powder and 10. Mu.l of 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in 0.1M PBS (pH 6.8) for 2 hours under the condition of potential range of-0.1V to 0.9V (vs. SCE), and then constant potential scanning is carried out for 30 minutes under the condition of 0V; after repeating the above operation for 3 times, the pretreated modified electrode was immersed in a 0.1M PBS solution for use.
The electrochemical test adopts a three-electrode system, wherein a PANI-Ag modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. In order to obtain stable and high-sensitivity electrochemical signals, the modified electrode is subjected to constant potential scanning for 30 seconds under the condition of 0V before each DPV test, so that the modified electrode material is in an electrochemical reduction state. The whole experiment was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Test example:
FIG. 1 is an SEM image of a PANI-based series of nanocatalysts; from the figure, the PANI nano-carrier is of a short fiber structure and has the diameter of 30-60nm; PANI-Cu synthesized by hydrothermal method 2 O nano catalyst, cu 2 O presents irregular particles of 100-300nm and is loaded on the surface of PANI; the PANI-Ag nano catalyst synthesized by a hydrothermal method has a long-chain bead structure with the diameter of about 100 nm; and after being compounded by the multicomponent material, cu 2 OAg nanomaterials morphologically incorporate Cu 2 O and Ag nano materials are characterized by an elongated ellipsoidal structure. Characterization by EDS, PANI-Cu 2 The elongated ellipsoidal nanomaterial loaded in the OAg nano catalyst is Cu 2 OAg two-component material, wherein Cu 2 O: the mass ratio of Ag is 1:1.PANI-Cu 2 OAg、PANI-Cu 2 The total mass of the metal or metal oxide load in O, PANI-Ag is 10%.
FIG. 2 shows PANI-Cu 2 DPV test pattern of OAg nanocatalyst modified electrode in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA; as can be seen from the graph, the oxidation current potential of DA ranges from 0.04V to 0.4V, and the oxidation peak potential is 0.17V; the oxidation current potential range of UA is 0.22V-0.64V, oxidation peak is 0.4V; AA has no significant electrochemical response signal under this test condition. Therefore, in the detection of a system in which DA, UA and AA coexist, the test method has good sensitivity and anti-interference capability on DA and UA.
FIG. 3 is a graph of DPV test of PANI-based series modified electrodes in 0.1M PBS (pH 6.8) solution containing 200. Mu.M DA; from the graph, the oxidation peak potential and the oxidation current potential range of DA on the PANI-based series modified electrode are greatly different. DA is in PANI-Cu in terms of detection sensitivity 2 The electrochemical response signal on the OAg modified electrode is obviously larger than that of PANI-Cu 2 O, PANI-Ag and PANI modified electrode has excellent electrocatalytic performance to DA.
Fig. 4 shows a PANI-based systemDPV test pattern of column modified electrode in 0.1M PBS (pH 6.8) solution containing 1mM UA; from the graph, the oxidation current potential range and the oxidation peak potential of UA on the PANI-based series modified electrode are greatly different. In the series of modified electrodes, UA is in PANI-Cu 2 Comparison of electrochemical response signals on OAg modified electrodes PANI-Cu 2 O, PANI-Ag and PANI modified electrode shows great enhancement and excellent electrocatalytic performance. It can be seen that PANI-Cu 2 OAg modified electrodes have excellent electrocatalytic properties to both DA and UA.
FIG. 5 is a PANI-Cu 2 DPV test patterns of OAg modified electrodes in 0.1M PBS (pH 6.8) solutions containing different concentrations of DA; from the graph, the oxidation current potential ranges of DA with different concentrations on the modified electrode are all 0.04V-0.4V, and oxidation peak potentials are all near 0.17V; as the concentration of DA increases, the electrochemical response signal of DA on the modified electrode increases, and the detection limit is 0.005. Mu.M. The concentration of DA in the extracellular fluid of healthy individuals is 0.01-1. Mu.M, while the normal concentration of DA in urine is 0.1-2. Mu.M. Therefore, the DA detection method provided by the invention has high enough sensitivity, can accurately detect the DA concentration in human body fluid, and is not interfered by UA and AA.
FIG. 6 shows DA in PANI-Cu 2 Standard curve for DPV test on OAg modified electrode; as can be seen from the graph, the concentration range of the detection of the present invention is 0.005. Mu.M to 200. Mu.M, and the DA concentration and the peak current show a bilinear relationship. The linear curve at high concentration (10. Mu.M-200. Mu.M) is y=0.0608x+2.0275, the correlation coefficient R 2 = 0.99771. At low concentrations (0.005 μm-10 μm) the linear curve is y=0.204x+0.364, the correlation coefficient R 2 =0.94276。
FIG. 7 is a PANI-Cu 2 DPV test patterns of OAg modified electrode in 0.1M PBS (pH 6.8) solution containing UA at different concentrations; from the graph, the oxidation current potential ranges of UA with different concentrations on the modified electrode are all 0.22V-0.64V, and oxidation peak potentials are all near 0.4V; as the UA concentration increases, the electrochemical response signal of UA on the modified electrode increases with the detection limit of 1 μm. UA concentration in serum of healthy human body is 120-460 mu M, the inventionThe provided method has enough sensitivity, can be used for detecting UA in human serum, and is not interfered by DA and AA.
FIG. 8 shows UA in PANI-Cu 2 Standard curve for DPV test on OAg modified electrode. As can be seen from the graph, the linear relation between the concentration of UA and the peak current is shown in the detection linear concentration range of 1 mu M-500 mu M, the linear curve is y=0.0211x+0.6490, and the correlation coefficient is R 2 =0.99138。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite is characterized by comprising the following steps of:
s1: adding 0.5mL of aniline monomer into 50mL of dichloromethane solution, and carrying out ultrasonic treatment to uniformly disperse the aniline monomer to form transparent uniform organic phase solution;
s2: sequentially adding 50mL of 0.2mol/L N-methyl pyrrolidone aqueous solution and 2.323g camphorsulfonic acid into the organic phase solution under the stirring condition, stirring at room temperature for 20-30min, and standing;
s3: slowly adding 5mL of 0.06g/mL ammonium persulfate aqueous solution into the reaction solution prepared in the step S2, standing for reaction for 60-90min, separating dichloromethane at the lower layer, and filtering the residual solution through a mixed system filter membrane to obtain a solid product;
s4: washing and drying the solid product to obtain camphorsulfonic acid doped PANI nano powder;
s5: dissolving 400mg of camphorsulfonic acid doped PANI nano powder in 5ml of 0.1M PBS solution by ultrasonic, adding 25ml of ethylene glycol, fully mixing, adding 75mg of copper sulfate pentahydrate and 3.77ml of 47.93mM silver acetate solution, and fully mixing to obtain PANI nano composite material precursor solution;
s6: dissolving 0.1g of NaOH and 3g of glucose in 5ml of 0.1M PBS solution, adding the solution into the PANI nanocomposite precursor solution, uniformly mixing, heating at 120 ℃ for reaction for 3-4 hours, filtering the product after the reaction by a mixed filter membrane, washing the filtered solid product, and drying to obtain the PANI nanocomposite powder.
2. The method for preparing the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite according to claim 1, wherein the specific step of S4 is as follows: washing the solid product with distilled water and ethanol in turn, cleaning the filtered product, and naturally airing to obtain camphorsulfonic acid doped PANI nano powder.
3. The preparation method of the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode is characterized by comprising the following steps of:
1): polishing the glassy carbon electrode on a polishing pad by using alumina slurry with the particle diameters of 3 mu m, 1 mu m, 0.3 mu m and 0.05 mu m in sequence, washing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use;
2): adding 2mg of the PANI nanocomposite powder prepared by the method of any one of claims 1-2 and 10 μl of 5% Nafion ethanol solution into 0.5ml of ethanol, and performing ultrasonic dispersion to form a uniform mixed suspension;
3): and (3) dripping 20 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing to obtain the PANI nanocomposite modified electrode.
4. The method for preparing the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode according to claim 3, further comprising performing cyclic voltammetry scanning on the prepared PANI nanocomposite modified electrode under the conditions of 0.1M PBS and a potential range of-0.1V to 0.9V for 2 hours, and then performing constant potential scanning under the condition of 0V for 30 minutes; after repeating the above operation 3 times, the modified electrode after the treatment was immersed in a 0.1M PBS solution for use.
5. The polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode is characterized in that the polyaniline-loaded silver/cuprous oxide multi-element nanocomposite modified electrode is prepared by the method of any one of claims 3-4; the electrochemical test environment is as follows: the PANI nanocomposite material modified electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the pulse voltammetry test is carried out, the potential range of the pulse voltammetry test is-0.1V-0.9V, the scanning amplitude is 50mV, the pulse width is 50ms, and the pulse voltammetry test is carried out in a 0.1M PBS solution with pH=6.8.
6. The polyaniline loaded silver/cuprous oxide multi-element nanocomposite modified electrode as claimed in claim 5 wherein the modified electrode was scanned for 30s at constant potential at 0V prior to each pulsed voltammetry test.
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