CN102539510A - Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode - Google Patents
Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode Download PDFInfo
- Publication number
- CN102539510A CN102539510A CN2012100067873A CN201210006787A CN102539510A CN 102539510 A CN102539510 A CN 102539510A CN 2012100067873 A CN2012100067873 A CN 2012100067873A CN 201210006787 A CN201210006787 A CN 201210006787A CN 102539510 A CN102539510 A CN 102539510A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- electrode
- carbon electrode
- glassy carbon
- cobalt ferrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a method for determining hydrogen peroxide by using a nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode. The nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode is prepared and is used as a hydrogen peroxide electrochemical sensor to detect the concentration of hydrogen peroxide. By using electrochemical catalysis of perovskite, electrochemical catalysis is generated to the oxidization of the hydrogen peroxide under the condition that enzymes are not used. Not only can the defects of inactivation and instability under the condition that enzymes exist be avoided, but also the modified electrode greatly improves the analysis and detection sensitivity of the content of the hydrogen peroxide. The modified electrode is a novel electrochemical sensor. When the modified electrode is used for actual sample determination, the modified electrode has the characteristics of rapidness, high sensitivity, high accuracy and the like. The testing method provided by the invention has high repeatability and stability. The preparation method of the novel modified glassy carbon electrode has the advantages of low cost, simplicity, rapidness, easiness in operation and the like.
Description
Technical field
The present invention relates to a kind of method of utilizing inorganic calcium titanium ore nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode as hydrogen peroxide electrochemical sensor fast measuring superoxol, belong to electrochemical analysis detection technique field.
Background technology
Perovskite composite oxide is because of having natural perovskite (CaTi0
3) crystal structure and gaining the name, often with general formula ABO
3Expression, desirable perofskite type oxide (ABO
3) be cubic structure.At ABO
3In the type perovskite structure, A
2+And O
2 –The approximate cubic closest packing of common formation, each A
2+L2 oxygen coordination arranged, 0
2 –Belong to 8 BO simultaneously
6Octahedron, each is 0 years old
2 –There are 6 kations (4 A with 2 B) to be connected B
2+6 oxygen coordinations are arranged, in occupation of 0
2 –The whole oxygen octahedras space that forms.Perovskite composite oxide ABO
3Be a kind of novel inorganic nonmetallic materials with unique physical character and chemical property; The A position generally is rare earth or alkaline earth element ion; The B position is the transitional element ion; A position and B position all can partly be replaced and keep its crystal structure constant basically by other close metallic ions of radius, and therefore it is the desirable sample of research catalyst surface and catalytic performance in theory.Because this compounds has the electromagnetic performance of stable crystal structure, uniqueness as a kind of new-type functional material, has very big potentiality to be exploited in fields such as environmental protection and Industrial Catalysis.Perovskite nickel titanate lanthanum load cobalt ferrite promptly is a kind of inorganic perovskite material of specific composition wherein; Characteristics such as the catalysis that therefore has general perovskite and had, conduction; It is modified at electrode surface has good electrochemical catalysis performance, can directly be used for the making of hydrogen peroxide electrochemical sensor.
Hydrogen peroxide is a kind of strong oxidizer, is applicable to wound disinfection and environment, food sterilization.Up to the present, the method for mensuration hydrogen peroxide mainly contains AAS, titrimetry and electrochemical method etc.Electrochemical method is because its analysis speed is fast, and cost is low, and advantage such as sensitivity height has received common concern.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of inorganic calcium titanium ore nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode and as the hydrogen peroxide electrochemical sensor, and the method that hydrogen peroxide is detected.
A kind of method with nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode mensuration hydrogen peroxide of the present invention is characterized in that having following process and step:
A. the pre-service of glass-carbon electrode: be that glass-carbon electrode is used 0.05 mmAl at first with glassy carbon electrodes
2O
3Burnishing powder and polishing flannelet polish said glass-carbon electrode, are polished to minute surface, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, for use then successively;
B. the preparation of nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode: at first dispose certain density nickel titanate lanthanum/cobalt ferrite suspension with redistilled water; Ratio between two is 20:1; Optimum concentration is 0.5～2.5 mg/mL, and at room temperature sonic oscillation is 24 hours; On the glass-carbon electrode surface of handling well, drip above-mentioned nickel titanate lanthanum/cobalt ferrite suspension 5 mL; Be positioned over then under the infrared lamp and dry, about 15 minutes; At room temperature place half an hour after drying; Fall residue with the second distillation water wash subsequently; Then in the sodium hydroxide solution of 0.1 M; in the potential window of – 1～1 V, be scanned up to stablely with cyclic voltammetry, use the second distillation water wash clean then, finally make nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode;
C. nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode detects concentration of hydrogen peroxide as the hydrogen peroxide electrochemical sensor: said modified glassy carbon electrode can directly be used for the electrochemical gaging of hydrogen peroxide; Its assay method is following: with described nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinized platinum electrode as auxiliary electrode, form three-electrode system; The 0.1 M NaOH solution ， that when measuring hydrogen peroxide three-electrode system is placed 10 mL from – 1 V to the potential range of 1 V in 20 sections of cyclic voltammetry scannings with activated electrode; On working electrode, apply certain anode potential then, note electric current-time curve, after background current reaches stable state, in 0.1 M NaOH solution, add the hydrogen peroxide standard solution with microsyringe; Under different superoxol concentration, record the current-responsive value of sensor, and in concentration 0.1 μ M～8.2mM scope, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, its linearly dependent coefficient hydrogen peroxide
r=0.997, utilize calibration curve method that hydrogen peroxide is carried out analyzing and testing.
Advantage of the present invention and characteristics are described below:
The present invention has utilized the electrocatalysis of perovskite; Oxidation to hydrogen peroxide under without the condition of enzyme has produced the electrochemical catalysis effect; Not only avoided the unsettled shortcoming of inactivation under the enzyme existence condition, and this modified electrode has improved the sensitivity of analyzing and testing concentration of hydrogen peroxide greatly.
Modified electrode among the present invention is a kind of novel electrochemical sensor, is used for actual sample and measures, and has characteristics such as quick, sensitive, accurate.Method of testing of the present invention has good reappearance and stability.The preparation method of the novel modified glassy carbon electrode among the present invention has advantages such as cost is low, simply quick, easy to operate.
Description of drawings
Fig. 1 among the present invention in the 0.1 M sodium hydroxide solution that contains superoxol (0.1 M) cyclic voltammogram on naked glass-carbon electrode (b), nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode (a);
Fig. 2 is under agitation add the naked glass-carbon electrode (a) of superoxol (0.1 M), the electricity stream – time curve of nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode (b) successively in 0.1 M sodium hydroxide solution among the present invention;
Fig. 3 is under the top condition, adds the electric current-time plot of the hydrogen peroxide standard solution of variable concentrations.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment:The preparation method and the step of the modified glassy carbon electrode in the present embodiment are following:
(1) pre-service of glass-carbon electrode: be that glass-carbon electrode is used 0.05 mmAl at first with glassy carbon electrodes
2O
3Burnishing powder and polishing flannelet polish said glass-carbon electrode, are polished to minute surface, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, for use then successively;
(2) preparation of perovskite nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode: at first dispose certain density nickel titanate lanthanum load cobalt ferrite suspension with redistilled water; Ratio between two is 20:1; Optimum concentration is 0.5～2.5mg/mL, and at room temperature sonic oscillation is 24 hours; On the glass-carbon electrode surface of handling well, drip above-mentioned nickel titanate lanthanum load cobalt ferrite suspension 5 mL; Be positioned over then under the infrared lamp and dry, about 15 minutes; At room temperature place half an hour after drying; Fall residue with the second distillation water wash subsequently; Then in the sodium hydroxide solution of 0.1 M; in the potential window of – 1～1 V, be scanned up to stablely with cyclic voltammetry, use the second distillation water wash clean then, finally make nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode (being nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode).
Nickel titanate lanthanum load cobalt ferrite (nickel titanate lanthanum/cobalt ferrite) modified glassy carbon electrode is to the electrochemical gaging of hydrogen peroxide:
Assay method is following: with described nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinized platinum electrode as auxiliary electrode, form three-electrode system; The 0.1 M NaOH solution ， that when measuring hydrogen peroxide three-electrode system is placed 10 mL from – 1 V to the potential range of 1 V in 20 sections of cyclic voltammetry scannings with activated electrode; On working electrode, apply certain anode potential then, note electric current-time curve, after background current reaches stable state, in 0.1 M NaOH solution, add the hydrogen peroxide standard solution with microsyringe; Under different superoxol concentration, record the current-responsive value of sensor, and in concentration 0.1 μ M～8.2 mM scopes, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, its linearly dependent coefficient hydrogen peroxide
r=0.997, utilize calibration curve method that hydrogen peroxide is carried out analyzing and testing.
Catalytic action as the modified glassy carbon electrode of hydrogen peroxide sensor characterizes:Cyclic voltammogram in the 0.1 M sodium hydroxide solution that contains superoxol (0.1 mM) on naked glass-carbon electrode (b), nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode (a) is as shown in Figure 1.As can be seen from the figure; Naked glass-carbon electrode does not almost change for the adding electric current of hydrogen peroxide; And nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode is after hydrogen peroxide adds; Peak current obviously strengthens on original basis, explains that modified electrode has tangible catalysed oxidn to hydrogen peroxide.Equally, under agitation, the hydrogen peroxide that in the NaOH of 0.1 M, adds 0.1 mM successively obtains Shi Jian – current curve as shown in Figure 2.Current-responsive is very little on bare electrode, but increases about 10 times at current-responsive on the modified electrode, so utilize this curve can show that also nickel titanate lanthanum load cobalt ferrite has good catalytic action.
The Electrochemical Detection hydrogen peroxide:Under best test condition, nickel titanate lanthanum load cobalt ferrite modified glassy carbon electrode to hydrogen peroxide the time between the – current-responsive as shown in Figure 3.Visible by figure, the time that reaches 98% steady-state current, the response time was very short less than 5s; Along with the increase of concentration of hydrogen peroxide, sensor increases the current-responsive of hydrogen peroxide gradually, in 0.1 mM ~ 8.2 mM scopes; Electric current and concentration of hydrogen peroxide are linear, and be as shown in Figure 3.Linear equation is I (mA)=0.2246C (mM)+14.938, and linearly dependent coefficient is 0.997.
The electrode of the inventive method preparation, reappearance with have good stability.For hydrogen peroxide sensor, the standard deviation of 11 replications is 2.3%.Electrode not the time spent 4 ℃ deposit a week after, current-responsive still remains 95% of initial current.And 10 times indium, metallic ions such as chromium, 5 times nickel has slight interference; 50 times of citric acids, 10 times magnesium ion is interference measurement hardly, and 5 times copper ion is bigger to measuring interference.Its lowest detection is limited to 23.5 nM.
Claims (1)
1. measure the method for hydrogen peroxide with nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode for one kind, it is characterized in that having following process and step:
A. the pre-service of glass-carbon electrode: be that glass-carbon electrode is with 0.05 mm Al at first with glassy carbon electrodes
2O
3Burnishing powder and polishing flannelet polish said glass-carbon electrode, are polished to minute surface, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, for use then successively;
B. the preparation of perovskite nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode: at first dispose certain density nickel titanate lanthanum load cobalt ferrite suspension with redistilled water; Ratio between two is 20:1; Optimum concentration is 0.5～2.5 mg/mL, and at room temperature sonic oscillation is 24 hours; On the glass-carbon electrode surface of handling well, drip above-mentioned nickel titanate lanthanum/cobalt ferrite suspension 5 mL; Be positioned over then under the infrared lamp and dry, about 15 minutes; At room temperature place half an hour after drying; Fall residue with the second distillation water wash subsequently; Then in the sodium hydroxide solution of 0.1 M; in the potential window of – 1～1 V, be scanned up to stablely with cyclic voltammetry, use the second distillation water wash clean then, finally make nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode;
C. nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode detects concentration of hydrogen peroxide as the hydrogen peroxide electrochemical sensor: said modified glassy carbon electrode can directly be used for the electrochemical gaging of hydrogen peroxide; Its assay method is following: with described nickel titanate lanthanum/cobalt ferrite modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinized platinum electrode as auxiliary electrode, form three-electrode system; The 0.1 M NaOH solution ， that when measuring hydrogen peroxide three-electrode system is placed 10 mL from – 1 V to the potential range of 1 V in 20 sections of cyclic voltammetry scannings with activated electrode; On working electrode, apply certain anode potential then, note electric current-time curve, after background current reaches stable state, in 0.1 M NaOH solution, add the hydrogen peroxide standard solution with microsyringe; Under different superoxol concentration, record the current-responsive value of sensor, and in concentration 0.1 μ M～8.2 mM scopes, obtain the linear relationship curve of electric current and concentration of hydrogen peroxide, its linearly dependent coefficient hydrogen peroxide
r=0.997, utilize calibration curve method that hydrogen peroxide is carried out analyzing and testing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100067873A CN102539510A (en) | 2012-01-11 | 2012-01-11 | Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100067873A CN102539510A (en) | 2012-01-11 | 2012-01-11 | Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102539510A true CN102539510A (en) | 2012-07-04 |
Family
ID=46346921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100067873A Pending CN102539510A (en) | 2012-01-11 | 2012-01-11 | Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102539510A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN113433187A (en) * | 2021-07-01 | 2021-09-24 | 常州大学 | LaMnO3Electrochemical sensor of chitosan non-enzymatic hydrogen peroxide and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6042714A (en) * | 1997-05-02 | 2000-03-28 | National Science Council | Method and chemical sensor for determining concentrations of hydrogen peroxide and its precursor in a liquid |
| CN102175728A (en) * | 2011-01-18 | 2011-09-07 | 兰州大学 | Method for preparing nanometer Co-Fe prussian-blue complex-carbon nano tube composite hydrogen peroxide sensor |
-
2012
- 2012-01-11 CN CN2012100067873A patent/CN102539510A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6042714A (en) * | 1997-05-02 | 2000-03-28 | National Science Council | Method and chemical sensor for determining concentrations of hydrogen peroxide and its precursor in a liquid |
| CN102175728A (en) * | 2011-01-18 | 2011-09-07 | 兰州大学 | Method for preparing nanometer Co-Fe prussian-blue complex-carbon nano tube composite hydrogen peroxide sensor |
Non-Patent Citations (1)
| Title |
|---|
| DAXIN YE ET AL: "A novel nonenzymatic hydrogen peroxide sensor based on LaNi0.5Ti0.5O3/CoFe2O4 modified electrode", 《COLLOIDS AND SURFACES B:BIOINTERFACES》, vol. 89, 22 August 2011 (2011-08-22), pages 10 - 14 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN113433187A (en) * | 2021-07-01 | 2021-09-24 | 常州大学 | LaMnO3Electrochemical sensor of chitosan non-enzymatic hydrogen peroxide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kurzweil | Metal oxides and ion-exchanging surfaces as pH sensors in liquids: State-of-the-art and outlook | |
| Yi et al. | Adsorption stripping voltammetry of phenol at Nafion-modified glassy carbon electrode in the presence of surfactants | |
| CN110779974B (en) | Novel enzyme-free glucose sensor applied to in-situ detection in fermentation process | |
| Tashkhourian et al. | Simultaneous determination of tyrosine and tryptophan by mesoporous silica nanoparticles modified carbon paste electrode using H-point standard addition method | |
| Mazloum-Ardakani et al. | Simultaneous and selective voltammetric determination of epinephrine, acetaminophen and folic acid at a ZrO2 nanoparticles modified carbon paste electrode | |
| Habibi et al. | Voltammetric determination of vitamin B 6 (pyridoxine) using multi wall carbon nanotube modified carbon-ceramic electrode | |
| Yuan et al. | Electrochemical determination of glutathione based on an electrodeposited nickel oxide nanoparticles-modified glassy carbon electrode | |
| CN102539510A (en) | Method for determining hydrogen peroxide by using nickel lanthanum titanate/cobalt ferrite modified glassy carbon electrode | |
| Ojani et al. | A New Voltammetric Sensor for Hydrazine Based on Michael Addition Reaction Using 1‐Amino‐2‐naphtol‐4‐sulfonic Acid | |
| CN106248770A (en) | A kind of electrochemical method of quick detection fenifrothion pesticide residues | |
| CN106442667A (en) | Method for detecting blood glucose by virtue of persimmon tannin@graphene@Pt-Pd non-enzymatic sensor | |
| Wang et al. | Direct electrochemical detection of pyruvic acid by cobalt oxyhydroxide modified indium tin oxide electrodes | |
| CN104569121A (en) | Method for detecting lead ion concentration in solution | |
| CN105738441A (en) | Modified glassy carbon electrode and preparation method and application thereof | |
| CN103149256A (en) | Electrochemical sensor prepared from SrNiFeO3-modified glassy carbon electrode and method for determining H2O2 with same | |
| Sobkowiak et al. | Amperometric detection of iron (III) on electroconductive hydrogel based on polypyrrole and alkoxysulfonated poly (3, 4-ethylenedioxythiophene)(PEDOT-S) | |
| CN102128865A (en) | Method for detecting phenol compounds by using horseradish peroxidase-modified electrode | |
| CN103308580A (en) | Novel use of porphyrin modified electrode | |
| CN103558269A (en) | Preparation method of enzyme sensor for detecting chlorpyrifos pesticide residues | |
| Zhao et al. | Electrochemically reduced graphene oxide modified screen-printed electrodes for sensitive determination of acetylsalicylic acid | |
| CN103940861A (en) | Method of detecting endocrine disrupting chemicals by adoption of nucleic acid aptamer visible-light electrode | |
| Zimer et al. | Needle-like IrO/Ag combined pH microelectrode | |
| CN102095779A (en) | Method for measuring concentration of glucose solution by carbon paste electrode modified by lanthanum-doped nickel titanate | |
| Sun et al. | Hybridization-induced Ag (I) dissociation from an immobilization-free and label-free hairpin DNA: toward a novel electronic monitoring platform | |
| WO2014091083A1 (en) | A reference electrode and an arrangement for an electrochemical measurement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |