CN111103340A - Preparation method and application of glassy carbon electrode modified by nano particles - Google Patents
Preparation method and application of glassy carbon electrode modified by nano particles Download PDFInfo
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- CN111103340A CN111103340A CN201911174291.5A CN201911174291A CN111103340A CN 111103340 A CN111103340 A CN 111103340A CN 201911174291 A CN201911174291 A CN 201911174291A CN 111103340 A CN111103340 A CN 111103340A
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- 229910021397 glassy carbon Inorganic materials 0.000 title claims abstract description 76
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 108
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims abstract description 82
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 54
- 239000002086 nanomaterial Substances 0.000 claims abstract description 52
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229960002477 riboflavin Drugs 0.000 claims abstract description 42
- 235000019192 riboflavin Nutrition 0.000 claims abstract description 40
- 239000002151 riboflavin Substances 0.000 claims abstract description 40
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 33
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 33
- 229920000123 polythiophene Polymers 0.000 claims abstract description 23
- 238000001903 differential pulse voltammetry Methods 0.000 claims abstract description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 238000000835 electrochemical detection Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229930003471 Vitamin B2 Natural products 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 235000019164 vitamin B2 Nutrition 0.000 description 2
- 239000011716 vitamin B2 Substances 0.000 description 2
- 206010010741 Conjunctivitis Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000005232 Glossitis Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
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- 201000003465 angular cheilitis Diseases 0.000 description 1
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- 208000007287 cheilitis Diseases 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 210000004392 genitalia Anatomy 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
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- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
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- 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
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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
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention discloses a preparation method of a glassy carbon electrode modified by nano particles and application of the electrode in electrochemical detection of riboflavin. The detection method of the invention deposits platinum nano particles on the surface of a glassy carbon electrode in chloroplatinic acid solution by cyclic voltammetry, and synthesizes MoS by hydrothermal synthesis2Nano material of MoS2Modifying the surface of a glassy carbon electrode modified by platinum nanoparticles by using a nano material, and performing electrochemical polymerization on the surface of the glassy carbon electrode modified by the platinum nanoparticles2Electrically depositing polythiophene on the surface of the nano material to obtain polythiophene/MoS2The glass carbon electrode is modified by nano materials/platinum nano particles. The differential pulse voltammetry is adopted to detect the riboflavin, the linear range is wide, the sensitivity is high, the electrode can be used for many times, and the operation is convenient.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis, in particular to a preparation method of a nano particle modified glassy carbon electrode and application of the nano particle modified glassy carbon electrode to the electrochemical detection of riboflavin.
Background
Riboflavin, also known as vitamin B2, is sparingly soluble in water, is stable when heated in neutral or acidic solutions, is a component of the prosthetic group of enzymes in the body (xanthases exert their hydrogen-transferring action in biological redox), and in the absence of this, affects biological oxidation of the body and prevents metabolism. The pathological changes are mostly shown as inflammation of the mouth, eyes and external genitalia, such as angular cheilitis, glossitis, conjunctivitis, scrotitis and the like, so the riboflavin can be used for preventing and treating the diseases.
In the prior art, the detection method of riboflavin mainly adopts HPLC combined with ultraviolet detection, for example, Licaixia et al adopts C18 column, uses 0.005 mol.L-1 sodium heptanesulfonate solution (containing 0.5% glacial acetic acid and 0.05% triethylamine) -methanol (65:35, v: v) as mobile phase, and has flow rate of 1.0m L min-1And the ultraviolet detection wavelength is 280nm, and the contents of vitamin B1, vitamin B2 and vitamin B6 in the vitamin B tablets are detected. (Li Caixia et al, strait pharmacology, 6 th 2017).
However, the HPLC method requires a complicated pretreatment step, requires expensive equipment, and requires a complicated detection process. Compared with HPLC method, the electrochemical analysis method has the advantages of good selectivity, high sensitivity, less time consumption, low detection limit, fast response speed and the like, and does not need expensive instruments. Based on polythiophene/MoS2The method for detecting riboflavin by using the glass carbon electrode modified by the nano material/platinum nanoparticles is not reported.
Disclosure of Invention
The invention aims to solve the problems of complex process, long time consumption and the like of riboflavin analysis by methods such as HPLC (high performance liquid chromatography) and the like, and provides a preparation method of a nano particle modified glassy carbon electrode, which can be used for rapidly detecting riboflavin in a solution by applying the glassy carbon electrode to the electrochemical detection of riboflavin, and has the advantages of wide linear range, high sensitivity, repeated use of the electrode and convenient operation.
The purpose of the invention is realized as follows:
(1) pretreating a glassy carbon electrode: sequentially placing a glassy carbon electrode on polishing cloth containing polishing powder with the particle sizes of 1 mu m, 0.3 mu m and 0.05 mu m to polish the glassy carbon electrode to a mirror surface, sequentially placing the glassy carbon electrode in acetone, a sulfuric acid solution with the concentration of 0.5mol/L and ultrapure water to perform ultrasonic treatment for 1 minute, and washing the glassy carbon electrode with the ultrapure water for 1 minute after each ultrasonic treatment to obtain a pretreated glassy carbon electrode;
(2) preparing a platinum nanoparticle modified glassy carbon electrode: placing the pretreated glassy carbon electrode in a hydrogen-containing atmosphere2PtCl6(100mM) potential sweep range-0.8Performing electrodeposition of platinum nanoparticles by cyclic voltammetry at V-0V, washing with ethanol and deionized water after the electrodeposition is finished, and drying under an infrared lamp to obtain a platinum nanoparticle modified glassy carbon electrode;
(3)MoS2preparing a nano material: 0.7mmol (NH)4)6Mo7O24·4H2Dissolving O in 20mL of deionized water by ultrasonic waves, slowly adding 10mg of surfactant-citric acid monohydrate under the condition of magnetic stirring, and continuously stirring for 30min to uniformly mix to obtain a solution A; then, adding 10mmol of thiourea into 20mL of deionized water, and carrying out ultrasonic dissolution to obtain a solution B; slowly dripping the solution B into the solution A under the conditions of room temperature and vigorous stirring, continuously stirring for 1 hour after dripping is finished, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 180 ℃ and 200 ℃ for 20-24 hours, naturally cooling to room temperature after the reaction is finished, filtering to obtain a solid product, washing the obtained solid product with ethanol and carbon disulfide for a plurality of times, placing the product in a vacuum drying box for drying at the temperature of 50 ℃ overnight to obtain MoS2A nanomaterial; the electron microscope analysis result shows that the molybdenum sulfide nano material has a porous spherical shape.
(4) The obtained MoS2Dispersing 200-300mg of the nano material in 20mL of deionized water containing 0.5% of Nafion by ultrasonic for 5min, dripping 20 mu L of the nano material on the surface of the glassy carbon electrode modified by the platinum nano particles obtained in the step (2), and airing to obtain MoS2Modifying the glassy carbon electrode by the nano material/platinum nano particles;
(5) with the MoS2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in an aqueous solution containing thiophene monomers, electrochemical polymerization is carried out by cyclic voltammetry, polythiophene is modified on the working electrode, and polythiophene/MoS is obtained2The glass carbon electrode is modified by nano materials/platinum nano particles.
Further, the concentration of the chloroplatinic acid solution in the step (2) is 200 mM.
Further, the potential scanning range of the electrochemical deposition in the step (2) is-0.8V-0V.
Further, the conditions of the hydrothermal reaction in the step (3) are as follows: carrying out hydrothermal reaction at 200 ℃ for 24 h.
Further, in the step (4), 300mgMoS is added2The nanomaterial was ultrasonically dispersed in 20mL of deionized water containing 0.5% Nafion.
The invention also provides polythiophene/MoS2Application of nano material/platinum nano particle modified glassy carbon electrode and polythiophene/MoS2The nano material/platinum nano particle modified glassy carbon electrode is prepared by adopting any one of the methods; the application is to mix polythiophene/MoS2The nano material/platinum nano particle modified glassy carbon electrode is applied to electrochemical detection of riboflavin.
Further, the step of electrochemically detecting riboflavin comprises:
a. preparing riboflavin aqueous solutions with different concentrations by adopting PBS buffer solution;
b. by using polythiophene/MoS2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, and the three-electrode system is placed in a riboflavin water solution;
c. carrying out electrochemical detection on riboflavin by adopting a differential pulse voltammetry method to obtain peak currents corresponding to riboflavin with different concentrations;
d. taking the peak current as a vertical coordinate and the concentration as a horizontal coordinate to make a standard curve;
e. and (3) placing the three-electrode system in the riboflavin aqueous solution with unknown concentration to obtain a differential pulse voltammetry curve and a peak current of the riboflavin aqueous solution with unknown concentration, and obtaining the riboflavin concentration according to a standard curve.
Further, the concentrations of the riboflavin aqueous solutions with different concentrations are respectively as follows: 1.0X 10-7mol/L，1.0×10-6mol/L，2.0×10-6mol/L，5.0×10-6mol/L，8.0×10-6mol/L，1.0×10-5mol/L。
Further, the electrochemical parameters of the differential pulse voltammetry are as follows: the scanning potential range is 0.5-1.0V, and the scanning speed is 100 mV/s.
Further, the detection limit of the differential pulse voltammetry for detecting the riboflavin is 6.0 multiplied by 10-8mol/L, linear range of 1.0X 10-7mol/L-8.0×10-6mol/L。
Compared with the prior art, the electrode prepared by the invention for detecting the riboflavin electrochemically has the advantages of simple equipment, convenient operation and short detection time compared with other methods for detecting the riboflavin; MoS formed as a result of the preparation according to the invention2The nano material has a porous spherical structure, and the platinum nanoparticles are modified on the electrode, so that excellent conductivity and extremely high specific surface area of the electrode are provided, and electrochemical polymerization of the polythiophene material can be formed in the porous spherical structure, so that the catalytic effect of the electrode is greatly improved, and the electrode prepared by the method has the advantages of high sensitivity, wide linear range and high accuracy when used for detecting riboflavin.
Drawings
FIG. 1 is a polythiophene/MoS2And detecting riboflavin by using the nano material/platinum nano particle modified glassy carbon electrode to obtain a peak current-concentration standard curve.
Detailed Description
The invention is further described with reference to the accompanying drawings, which are not intended to be limiting in any way, and any variations based on the teachings of the invention are intended to fall within the scope of the invention.
Example 1
(1) Pretreating a glassy carbon electrode: sequentially placing a glassy carbon electrode on polishing cloth containing polishing powder with the particle sizes of 1 mu m, 0.3 mu m and 0.05 mu m to polish the glassy carbon electrode to a mirror surface, sequentially placing the glassy carbon electrode in acetone, a sulfuric acid solution with the concentration of 0.5mol/L and ultrapure water to perform ultrasonic treatment for 1 minute, and washing the glassy carbon electrode with the ultrapure water for 1 minute after each ultrasonic treatment to obtain a pretreated glassy carbon electrode;
(2) preparing a platinum nanoparticle modified glassy carbon electrode: placing the pretreated glassy carbon electrode in a hydrogen-containing atmosphere2PtCl6Performing electrodeposition of platinum nanoparticles in (100mM) solution by cyclic voltammetry under potential scanning range of-0.8V-0V, washing with ethanol and deionized water after deposition, and drying under infrared lamp to obtain the final productModifying a glassy carbon electrode by using platinum nanoparticles;
(3)MoS2preparing a nano material: 0.7mmol (NH)4)6Mo7O24·4H2Dissolving O in 20mL of deionized water by ultrasonic waves, slowly adding 10mg of surfactant-citric acid monohydrate under the condition of magnetic stirring, and continuously stirring for 30min to uniformly mix to obtain a solution A; then, adding 10mmol of thiourea into 20mL of deionized water, and carrying out ultrasonic dissolution to obtain a solution B; slowly dropwise adding the solution B into the solution A under the conditions of room temperature and vigorous stirring, continuously stirring for 1 hour after dropwise adding is finished, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction at 180 ℃ for 20 hours, naturally cooling to room temperature after the reaction is finished, filtering to obtain a solid product, washing the obtained solid product with ethanol and carbon disulfide for a plurality of times, and drying the product in a vacuum drying oven at 50 ℃ overnight to obtain MoS2A nanomaterial; the electron microscope analysis result shows that the molybdenum sulfide nano material has a porous spherical shape.
(4) The obtained MoS2Ultrasonically dispersing 200mg of nano material in 20mL of deionized water containing 0.5% of Nafion for 5min, dropwise coating 20 mu L of nano material on the surface of the glassy carbon electrode modified by the platinum nano particles obtained in the step (2), and airing to obtain MoS2Modifying the glassy carbon electrode by the nano material/platinum nano particles;
(5) with the MoS2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in aqueous solution containing thiophene monomers, electrochemical polymerization is carried out by cyclic voltammetry, the potential range is-1.0V to-0.5V, polythiophene is modified on the working electrode, and polythiophene/MoS is obtained2The glass carbon electrode is modified by nano materials/platinum nano particles.
Example 2
(1) Pretreating a glassy carbon electrode: sequentially placing a glassy carbon electrode on polishing cloth containing polishing powder with the particle sizes of 1 mu m, 0.3 mu m and 0.05 mu m to polish the glassy carbon electrode to a mirror surface, sequentially placing the glassy carbon electrode in acetone, a sulfuric acid solution with the concentration of 0.5mol/L and ultrapure water to perform ultrasonic treatment for 1 minute, and washing the glassy carbon electrode with the ultrapure water for 1 minute after each ultrasonic treatment to obtain a pretreated glassy carbon electrode;
(2) preparing a platinum nanoparticle modified glassy carbon electrode: placing the pretreated glassy carbon electrode in a hydrogen-containing atmosphere2PtCl6Performing electrodeposition of platinum nanoparticles in a (100mM) solution by cyclic voltammetry under a potential scanning range of-0.8V-0V, washing with ethanol and deionized water after the electrodeposition is finished, and drying under an infrared lamp to obtain a platinum nanoparticle modified glassy carbon electrode;
(3)MoS2preparing a nano material: 0.7mmol (NH)4)6Mo7O24·4H2Dissolving O in 20mL of deionized water by ultrasonic waves, slowly adding 10mg of surfactant-citric acid monohydrate under the condition of magnetic stirring, and continuously stirring for 30min to uniformly mix to obtain a solution A; then, adding 10mmol of thiourea into 20mL of deionized water, and carrying out ultrasonic dissolution to obtain a solution B; slowly dropwise adding the solution B into the solution A under the conditions of room temperature and vigorous stirring, continuously stirring for 1 hour after dropwise adding is finished, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction at 200 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, filtering to obtain a solid product, washing the obtained solid product with ethanol and carbon disulfide for a plurality of times, and drying the product in a vacuum drying oven at 50 ℃ overnight to obtain MoS2A nanomaterial; the electron microscope analysis result shows that the molybdenum sulfide nano material has a porous spherical shape.
(4) The obtained MoS2Ultrasonically dispersing 300mg of nano material in 20mL of deionized water containing 0.5% of Nafion for 5min, dropwise coating 20 mu L of nano material on the surface of the glassy carbon electrode modified by the platinum nano particles obtained in the step (2), and airing to obtain MoS2Modifying the glassy carbon electrode by the nano material/platinum nano particles;
(5) with the MoS2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in aqueous solution containing thiophene monomers, electrochemical polymerization is carried out by cyclic voltammetry, the potential range is-1.0V to-0.5V, polythiophene is modified on the working electrode, and polythiophene/MoS is obtained2Nano materialThe glassy carbon electrode is modified by the material/platinum nano particles.
Example 3
The concentrations of the solutions were 1.0 × 10 in PBS buffer (pH 4.0), respectively-7mol/L，1.0×10-6mol/L，2.0×10-6mol/L，5.0×10-6mol/L，8.0×10-6mol/L，1.0×10-5A riboflavin water solution of mol/L; example 2 Polythiophene/MoS prepared2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, and the three-electrode system is placed in a riboflavin water solution;
the differential pulse voltammetry is adopted to carry out electrochemical detection on the riboflavin, the scanning potential range is 0.5-1.0V, and the scanning speed is 100 mV/s. The detection limit of differential pulse voltammetry for detecting riboflavin is 6.0 multiplied by 10-8mol/L, linear range of 1.0X 10-7mol/L-8.0×10-6mol/L。
In conclusion, the detection method disclosed by the invention deposits the platinum nanoparticles on the surface of the glassy carbon electrode in the chloroplatinic acid solution through cyclic voltammetry, and synthesizes MoS through a hydrothermal synthesis method2Nano material of MoS2Modifying the surface of a glassy carbon electrode modified by platinum nanoparticles by using a nano material, and performing electrochemical polymerization on the surface of the glassy carbon electrode modified by the platinum nanoparticles2Electrically depositing polythiophene on the surface of the nano material to obtain polythiophene/MoS2The glass carbon electrode is modified by nano materials/platinum nano particles. The differential pulse voltammetry is adopted to detect the riboflavin, the linear range is wide, the sensitivity is high, the electrode can be used for many times, and the operation is convenient.
The foregoing is directed to the preferred embodiment of the present invention and is not intended to limit the invention to the specific embodiment described. It will be apparent to those skilled in the art that various modifications, equivalents, improvements and the like can be made without departing from the spirit of the invention, and these are intended to be included within the scope of the invention.
Claims (9)
1. A preparation method of a glassy carbon electrode modified by nano particles is characterized by comprising the following steps:
(1) pretreating a glassy carbon electrode: sequentially placing a glassy carbon electrode on polishing cloth containing polishing powder with the particle sizes of 1 mu m, 0.3 mu m and 0.05 mu m to polish the glassy carbon electrode to a mirror surface, sequentially placing the glassy carbon electrode in acetone, a sulfuric acid solution with the concentration of 0.5mol/L and ultrapure water to perform ultrasonic treatment for 1 minute, and washing the glassy carbon electrode with the ultrapure water for 1 minute after each ultrasonic treatment to obtain a pretreated glassy carbon electrode;
(2) preparing a platinum nanoparticle modified glassy carbon electrode: placing the pretreated glassy carbon electrode in a hydrogen-containing atmosphere2PtCl6Performing electrodeposition of platinum nanoparticles in a (100mM) solution by cyclic voltammetry under a potential scanning range of-0.8V-0V, washing with ethanol and deionized water after the electrodeposition is finished, and drying under an infrared lamp to obtain a platinum nanoparticle modified glassy carbon electrode;
(3)MoS2preparing a nano material: 0.7mmol (NH)4)6Mo7O24·4H2Dissolving O in 20mL of deionized water by ultrasonic waves, slowly adding 10mg of surfactant-citric acid monohydrate under the condition of magnetic stirring, and continuously stirring for 30min to uniformly mix to obtain a solution A; then, adding 10mmol of thiourea into 20mL of deionized water, and carrying out ultrasonic dissolution to obtain a solution B; slowly dripping the solution B into the solution A under the conditions of room temperature and vigorous stirring, continuously stirring for 1 hour after dripping is finished, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 180 ℃ and 200 ℃ for 20-24 hours, naturally cooling to room temperature after the reaction is finished, filtering to obtain a solid product, washing the obtained solid product with ethanol and carbon disulfide for a plurality of times, placing the product in a vacuum drying box for drying at the temperature of 50 ℃ overnight to obtain MoS2A nanomaterial; an electron microscope analysis result shows that the molybdenum sulfide nano material has a porous spherical shape;
(4) the obtained MoS2Dispersing 200-300mg of the nano material in 20mL of deionized water containing 0.5% of Nafion by ultrasonic for 5min, dripping 20 mu L of the nano material on the surface of the glassy carbon electrode modified by the platinum nano particles obtained in the step (2), and airing to obtain MoS2Modifying the glassy carbon electrode by the nano material/platinum nano particles;
(5) to be provided withThe MoS2The nano material/platinum nano particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in an aqueous solution containing thiophene monomers, electrochemical polymerization is carried out by cyclic voltammetry, polythiophene is modified on the working electrode, and polythiophene/MoS is obtained2The glass carbon electrode is modified by nano materials/platinum nano particles.
2. The production method according to claim 1, wherein the concentration of the chloroplatinic acid solution in step (2) is 200 mM.
3. The method of claim 1, wherein the potential sweep range of the electrochemical deposition in step (2) is-0.8V-0V.
4. The method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out under the following conditions: carrying out hydrothermal reaction at 200 ℃ for 24 h.
5. The method according to claim 1, wherein the step (4) is carried out by mixing 300mgMoS2The nanomaterial was ultrasonically dispersed in 20mL of deionized water containing 0.5% Nafion.
6. The application of the glassy carbon electrode modified by the nano particles is characterized in that polythiophene/MoS2The nano material/platinum nano particle modified glassy carbon electrode is prepared by the method of any one of claims 1 to 5; the application is to mix polythiophene/MoS2The nano material/platinum nano particle modified glassy carbon electrode is applied to electrochemical detection of riboflavin.
7. The use of a nanoparticle-modified glassy carbon electrode according to claim 6, wherein: the step of electrochemically detecting riboflavin comprises:
a. preparing riboflavin aqueous solutions with different concentrations by adopting PBS buffer solution;
b. by using polythiophene/MoS2Nanomaterial/platinum nanoparticlesThe particle modified glassy carbon electrode is used as a working electrode, the platinum electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is placed in the riboflavin water solution;
c. carrying out electrochemical detection on riboflavin by adopting a differential pulse voltammetry method to obtain peak currents corresponding to riboflavin with different concentrations;
d. taking the peak current as a vertical coordinate and the concentration as a horizontal coordinate to make a standard curve;
e. and (3) placing the three-electrode system in the riboflavin aqueous solution with unknown concentration to obtain a differential pulse voltammetry curve and a peak current of the riboflavin aqueous solution with unknown concentration, and obtaining the riboflavin concentration according to a standard curve.
8. The use of a glassy carbon electrode modified with nanoparticles according to claim 7, wherein the electrochemical parameters of the differential pulse voltammetry are: the scanning potential range is 0.5-1.0V, and the scanning speed is 100 mV/s.
9. The application of the glassy carbon electrode modified by the nano particles as claimed in claim 8, wherein the detection limit of the differential pulse voltammetry for detecting the riboflavin is 6.0 x 10-8mol/L, linear range of 1.0X 10-7mol/L-8.0×10-6mol/L。
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