CN104458859A - La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode and preparation method and application thereof - Google Patents
La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode and preparation method and application thereof Download PDFInfo
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- CN104458859A CN104458859A CN201410763331.0A CN201410763331A CN104458859A CN 104458859 A CN104458859 A CN 104458859A CN 201410763331 A CN201410763331 A CN 201410763331A CN 104458859 A CN104458859 A CN 104458859A
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Abstract
The invention relates to an La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode and a preparation method and application thereof. The La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode can be used for carrying out sensitive quantitative analysis measurement on levulose by adopting a time-current curve method by utilizing the electrochemical catalytic oxidation effect of an La0.88Sr0.12MnO3 eletrospinning material on the levulose. The La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode is a three-electrode system which comprises a carbon paste modified electrode, a platinum electrode and a saturated calomel reference electrode. An experiment indicates that the modified electrode has the obvious catalytic oxidation effect on the levulose in 0.10mol/L NaOH supporting electrolyte, the levulose has a good linear relation with response current within a concentration range from 5.0*10<-8> to 1.0*10<-4>mol/L by adopting a current-time curve method under an optimum condition, and the detection limit reaches 2.2*10<-8> mol/L. The method is used for measuring the content of the levulose of injection liquid, and a result is satisfactory.
Description
Technical field
The present invention relates to a kind of La
0.88sr
0.12mnO
3carbon paste electrode that nanofiber is modified and its preparation method and application.
Background technology
Fructose is a kind of common monose, and it is the versatility sweetener of food_beverage industry, to its detection be and our life closely bound up.Although the absorption of fructose is very little on diabetes patient's impact, because its metabolic adsorption is fast, energy Synthesis triglyceride the same as glucose, undue absorption also can be causeed fat, high fat of blood, so be also very important to the detection of fructose.
Perovskite composite oxides ABO
3, have unique physical property and chemical property, it is at battery, solid electrolyte, and a lot of field of sensor is all widely used.After in standard perovskite, A or B position is replaced by other metallic ion or partly replaces, can form the B position ion of anion defect or different valence state, be a class excellent performance, broad-spectrum new function material.And the adulterated with Ca and Ti ore material of the nanofibrous structures of method of electrostatic spinning synthesis, is provided with the Common advantages of nanofiber and adulterated with Ca and Ti ore material especially, also will has simultaneously and more importantly apply.
At present, having Capillary Electrophoresis, high performance liquid chromatography MS, fluorometry, vapor-phase chromatography etc. to the method that fructose detects, there is the problems such as experimentation complexity, solvent toxicity be large, consuming time in these methods.Electrochemical Modification electrode method, due to advantages such as it are quick, accurate, sensitive, be easy to carry, is widely used in the detection of carbohydrate.And electrostatic spinning La
0.88sr
0.12mnO
3the detection of nanofiber decorating carbon paste electrode to fructose have not been reported.
Summary of the invention
An object of the present invention is to provide a kind of La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified.
Two of object of the present invention is to provide the preparation method of this carbon paste electrode and detecting the using method in fructose process as electrochemical sensor.
For achieving the above object, the present invention adopts following technical scheme:
A kind of La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified, is characterized in that this carbon paste electrode is La
0.88sr
0.12mnO
3nanofiber is modified at carbon paste electrode surface.
A kind ofly prepare above-mentioned La
0.88sr
0.12mnO
3the preparation method of the carbon paste electrode that nanofiber is modified, is characterized in that the concrete steps of the method are: by La
0.88sr
0.12mnO
3in nanofiber dispersion redistilled water, obtain dressing agent, wherein La
0.88sr
0.12mnO
3the mass volume ratio of nanofiber and redistilled water is: 2-8 mg mL
– 1, after ultrasonic disperse is even, this dressing agent is dripped and is coated in clean carbon paste electrode on the surface, dry, namely obtain La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified.
The preparation method of above-mentioned carbon paste electrode is: graphite and paraffin oil are mixed in mortar with the ratio of mass ratio 3:1, be stirred to evenly, then potpourri being loaded the glass tube that diameter is 3 mm, inserting copper wire to contacting with potpourri at the other end of glass tube.The graphite end of carbon paste electrode is polished on ganoid paper, namely obtains carbon paste electrode.
Above-mentioned La
0.88sr
0.12mnO
3the preparation method of nanofiber is:
The mixed in molar ratio of a. La salt, Sr salt and Mn salt being pressed La:Sr:Mn=0.88:0.12:1 forms slaine;
B. by step a gained slaine and PVP(polyvinylpyrrolidone) slowly join DMF(dimethyl formamide by after the mass ratio mixing of 1: 1-1: 2) in, stirred at ambient temperature 20-24 h, obtain the colloidal solution precursor with stickiness, its solid content is: 20-25%;
C. the precursor of step b gained is carried out electrostatic spinning, applied voltage is 10-15 kV, and syringe needle is 10-15 cm to the distance of receiver; After spinning completes, polymer fiber is put into drying box 70-80 DEG C of freeze-day with constant temperature 12-20 h; Dried fiber is calcined 2-3 h in the air atmosphere of 700-800 DEG C, and programming rate is 2-3 DEG C of min
– 1, obtain La
0.88sr
0.12mnO
3nanofiber.
An electrochemical determination method for fructose, adopts above-mentioned La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified, is characterized in that the concrete steps of this assay method are: by described La
0.88sr
0.12mnO
3nanofiber decorating carbon paste electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; During mensuration, three-electrode system is placed in the 0.15 mol L of 10 mL
– 1in NaOH solution, arranging initial voltage is 0.65 V, records electric current-time curve, after background current reaches stable state, adds fructose standard solution with microsyringe in NaOH solution; Under different fructose concentration, record the current-responsive value of sensor to them, concentration be 0.05 μM within the scope of 100.0 μMs, obtain the linear relationship curve of electric current and fructose concentration, its linearly dependent coefficient
r=0.999, utilize this calibration curve method to carry out analysis to fructose actual sample and detect.
Advantage and disadvantage of the present invention is as described below: present invention utilizes La
0.88sr
0.12mnO
3in Mn
3+and Mn
4+to the catalysed oxidn of fructose, the current-responsive of fructose on electrode is enlarged markedly, substantially increase the sensitivity analyzed and detect fructose concentration, this modified electrode is used for the mensuration of fructose content in fructose injection, result is satisfactory.
Modified electrode in the present invention is a kind of novel electrochemical sensor, measures, have the features such as quick, sensitive, accurate for actual sample.Method of testing of the present invention has good reappearance and stability.The preparation method of the decorating carbon paste electrode in the present invention has the advantages such as cost is low, simple and quick, easy to operate.
Accompanying drawing explanation
Fig. 1 is not containing 2.0 mM fructose and NaOH electrolyte solution (the 0.10 mol L containing 2.0 mM fructose solns in the present invention
– 1) at bare electrode (a, c), electrospinning La
0.88sr
0.12mnO
3cyclic voltammogram on nanofiber decorating carbon paste electrode (b, d).
Fig. 2 is under top condition, adds the current versus time curve figure of the fructose standard solution of variable concentrations, and illustration is the enlarged drawing of low concentration part.
Fig. 3 is under top condition, the concentration-current standard working curve diagram of fructose.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
Preparation method and the step of the modified electrode in the present embodiment are as follows:
(1). the preparation method of carbon paste electrode: graphite and paraffin oil are mixed in mortar with the ratio of mass ratio 3:1, is stirred to evenly, then potpourri is loaded the glass tube that diameter is 3 mm.Copper wire is inserted to contacting with potpourri at the other end of glass tube.The graphite end of carbon paste electrode is polished on ganoid paper, stand-by;
(2). electrospinning La
0.88sr
0.12mnO
3the preparation of nanofiber: 0.5272 g slaine (mol ratio La:Sr:Mn=0.88:0.12:1) and 0.5272 g PVP are slowly joined in 5 mL DMF, stirred at ambient temperature 20-24 h, obtain the colloidal solution precursor with stickiness.By in precursor inhalation syringe, metal needle connects high pressure and carries out electrostatic spinning, and applied voltage is 15 kV, and syringe needle is 15 cm to the distance of receiver.After spinning completes, polymer fiber is put into drying box 70 DEG C of freeze-day with constant temperature 12 h, finally dried fiber is put into tubular furnace, calcine 3 h in the air atmosphere of 800 DEG C, programming rate is 2 DEG C of min
– 1, obtain La
0.88sr
0.12mnO
3nanofiber.
(3) electrospinning La
0.88sr
0.12mnO
3the preparation of nanofiber decorating carbon paste electrode: by the La of certain mass
0.88sr
0.12mnO
3nanofiber dispersion is in 1 mL redistilled water, and ultrasonic disperse is even; Then get 10 μ L dressing agents to drip and be coated in clean carbon paste electrode on the surface, dry, stand-by under infrared lamp.
Electrospinning La
0.88sr
0.12mnO
3the purposes of nanofiber decorating carbon paste electrode and using method thereof:
(1) purposes of this modified electrode is directly used in fructose electrochemical gaging;
(2) this modified electrode using method and be determined as follows: described electrostatic spinning La
0.88sr
0.12mnO
3nanofiber decorating carbon paste electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; When measuring fructose, three-electrode system is placed in the 0.15 mol L of 10 mL
– 1in NaOH solution, best dressing agent concentration is 8 mg mL
– 1, arranging initial voltage is 0.65 V, records electric current-time curve, after background current reaches stable state, adds fructose standard solution with microsyringe in NaOH solution; Under different fructose concentration, record the current-responsive value of sensor to them, concentration be 0.05 μM within the scope of 100.0 μMs, obtain the linear relationship curve of electric current and fructose concentration, its linearly dependent coefficient
r=0.999.Calibration curve method can be utilized to carry out analysis to fructose actual sample detect.
catalytic action as the modified electrode of electrochemical sensor characterizes
Do not containing 2.0 mM fructose and NaOH electrolyte solution (the 0.10 mol L containing 2.0 mM fructose solns
– 1) at bare electrode (a, c), electrospinning La
0.88sr
0.12mnO
3cyclic voltammogram on nanofiber decorating carbon paste electrode (b, d) as shown in Figure 1.As can be seen from the figure, bare electrode cannot carry out detection to fructose and analyze, and La
0.88sr
0.12mnO
3nanofiber modified electrode is after fructose adds, and on original basis, oxidation peak current obviously strengthens, and illustrates that modified electrode has obvious catalysed oxidn to detection material.
electrochemical Detection fructose
Under optimum controlling condition, La
0.88sr
0.12mnO
3nanofiber decorating carbon paste electrode to add variable concentrations fructose standard solution Nong Du – current-responsive as shown in Figure 2.Along with the concentration of fructose increases, response current also increases gradually.As seen from Figure 3, concentration be 0.05 μM within the scope of 100.0 μMs, obtain the linear relationship curve of electric current and fructose concentration, linear equation is
i(μ A)=0.0335+0.1106
c(μM), its linearly dependent coefficient
r=0.999, detection limit can reach 22.3 nM.
Modified electrode prepared by the inventive method, reappearance and having good stability.10 replications, adrenergic standard deviation is 3.68%.Electrode is not after the used time deposits two weeks at 4 DEG C, and current-responsive remains 94.8% of initial current.Electrode prepared by the inventive method is not by the interference of the materials such as ascorbic acid, caffeine, phenylalanine, citric acid, sodium citrate, phosphoric acid, sodium chloride and sodium sulphate, and selectivity is good.
Utilize standard addition method to detect commercially available fructose injection, adopt the method that replicate determination is averaged for 3 times, the relative standard deviation of measurement result all can control within ± 5.0%.
Claims (5)
1. a La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified, is characterized in that this carbon paste electrode is La
0.88sr
0.12mnO
3nanofiber is modified at carbon paste electrode surface.
2. prepare the La belonging to claim 1 for one kind
0.88sr
0.12mnO
3the preparation method of the carbon paste electrode that nanofiber is modified, is characterized in that the concrete steps of the method are: by La
0.88sr
0.12mnO
3in nanofiber dispersion redistilled water, obtain dressing agent, wherein La
0.88sr
0.12mnO
3the mass volume ratio of nanofiber and redistilled water is: 2-8 mg mL
– 1, after ultrasonic disperse is even, this dressing agent is dripped and is coated in clean carbon paste electrode on the surface, dry, namely obtain La
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified.
3. method according to claim 2, it is characterized in that the preparation method of described carbon paste electrode is: graphite and paraffin oil are mixed in mortar with the ratio of mass ratio 3:1, be stirred to evenly, then potpourri is loaded the glass tube that diameter is 3 mm, copper wire is inserted to contacting with potpourri at the other end of glass tube
The graphite end of carbon paste electrode is polished on ganoid paper, namely obtains carbon paste electrode.
4. method according to claim 2, is characterized in that described La
0.88sr
0.12mnO
3the preparation method of nanofiber is:
The mixed in molar ratio of a. La salt, Sr salt and Mn salt being pressed La:Sr:Mn=0.88:0.12:1 forms slaine;
B. by step a gained slaine and polyvinylpyrrolidone PVP by slowly joining in dimethyl formamide DMF after the mass ratio mixing of 1: 1-1: 2, stirred at ambient temperature 20-24 h, obtain the colloidal solution precursor with stickiness, its solid content is: 20-25%;
C. the precursor of step b gained is carried out electrostatic spinning, applied voltage is 10-15 kV, and syringe needle is 10-15 cm to the distance of receiver; After spinning completes, polymer fiber is put into drying box 70-80 DEG C of freeze-day with constant temperature 12-20 h; Dried fiber is calcined 2-3 h in the air atmosphere of 700-800 DEG C, and programming rate is 2-3 DEG C of min
– 1, obtain La
0.88sr
0.12mnO
3nanofiber.
5. an electrochemical determination method for fructose, adopts La according to claim 1
0.88sr
0.12mnO
3the carbon paste electrode that nanofiber is modified, is characterized in that the concrete steps of this assay method are: by described La
0.88sr
0.12mnO
3nanofiber decorating carbon paste electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; During mensuration, three-electrode system is placed in the 0.15 mol L of 10 mL
– 1in NaOH solution, arranging initial voltage is 0.65 V, records electric current-time curve, after background current reaches stable state, adds fructose standard solution with microsyringe in NaOH solution; Under different fructose concentration, record the current-responsive value of sensor to them, concentration be 0.05 μM within the scope of 100.0 μMs, obtain the linear relationship curve of electric current and fructose concentration, its linearly dependent coefficient
r=0.999, utilize this calibration curve method to carry out analysis to fructose actual sample and detect.
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|---|---|---|---|
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|---|---|---|---|
| CN201410763331.0A CN104458859A (en) | 2014-12-12 | 2014-12-12 | La0.88Sr0.12MnO3 nano-fiber modified carbon paste electrode and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107367536A (en) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | A kind of preparation method of stable type carbon paste electrode |
| CN107860808A (en) * | 2017-11-08 | 2018-03-30 | 吉林大学 | With SrMnO3For the CeO of sensitive electrode2Benzylacetone sensor, preparation method and applications |
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| CN102095779A (en) * | 2010-11-28 | 2011-06-15 | 上海大学 | Method for measuring concentration of glucose solution by carbon paste electrode modified by lanthanum-doped nickel titanate |
| CN103149256A (en) * | 2013-02-27 | 2013-06-12 | 上海大学 | Electrochemical sensor prepared from SrNiFeO3-modified glassy carbon electrode and method for determining H2O2 with same |
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2014
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Patent Citations (4)
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| JP2000150288A (en) * | 1998-11-10 | 2000-05-30 | Hokuriku Electric Ind Co Ltd | Capacitor and its manufacture |
| CN1672284A (en) * | 2002-08-01 | 2005-09-21 | 圣安德鲁斯大学董事会 | Perovskite-based fuel cell electrode and membrane |
| CN102095779A (en) * | 2010-11-28 | 2011-06-15 | 上海大学 | Method for measuring concentration of glucose solution by carbon paste electrode modified by lanthanum-doped nickel titanate |
| CN103149256A (en) * | 2013-02-27 | 2013-06-12 | 上海大学 | Electrochemical sensor prepared from SrNiFeO3-modified glassy carbon electrode and method for determining H2O2 with same |
Non-Patent Citations (3)
| Title |
|---|
| DUO XU 等: "A novel nonenzymatic fructose sensor based on electrospun LaMnO3 fibers", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| YIXIN LIU 等: "La0.67Sr0.33MnO3 nanofibers for in situ, real-time, and stable high temperature oxygen sensing", 《RSC ADVANCES》 * |
| YULONG WANG 等: "A novel sensitive nonenzymatic glucose sensor based on perovskite LaNi0.5Ti0.5O3-modified carbon paste electrode", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107367536A (en) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | A kind of preparation method of stable type carbon paste electrode |
| CN107367536B (en) * | 2017-08-31 | 2019-10-29 | 东阳市天齐知识产权运营有限公司 | A kind of preparation method of stable type carbon paste electrode |
| CN107860808A (en) * | 2017-11-08 | 2018-03-30 | 吉林大学 | With SrMnO3For the CeO of sensitive electrode2Benzylacetone sensor, preparation method and applications |
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