CN103543188A - Electrochemical sensor for determining o-phenylenediamine with high flexibility as well as determining method of sensor - Google Patents

Electrochemical sensor for determining o-phenylenediamine with high flexibility as well as determining method of sensor Download PDF

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CN103543188A
CN103543188A CN201310471935.3A CN201310471935A CN103543188A CN 103543188 A CN103543188 A CN 103543188A CN 201310471935 A CN201310471935 A CN 201310471935A CN 103543188 A CN103543188 A CN 103543188A
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phenylenediamine
electrode
carbon electrode
lanitio
glassy carbon
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CN103543188B (en
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徐彦红
周英哲
辛美玲
黄岩
郑文玲
马文丽
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a preparation of a modified glassy carbon electrode by utilizing a novel perovskite composite nano material LaNiTiO3-Fe3O4 as well as an application of the modified glassy carbon electrode serving as an o-phenylenediamine electrochemical sensor to rapid and flexible determination of an o-phenylenediamine solution, and belongs to the technical field of nano science and technology and electrochemical analysis detection. The invention is mainly characterized in that by utilizing electrochemical catalysis and oxidation effects on o-phenylenediamine by the o-phenylenediamine sensor prepared from the LaNiTiO3-Fe3O4 turbid liquid modified glassy carbon electrode, the o-phenylenediamine is subjected to high-flexibility quantitative analysis testing through a square wave volt-ampere pulse method. According to the key points, a dispersed LaNiTiO3-Fe3O4 uniform turbid liquid is modified to the surface of the treated glassy carbon electrode by a dispensing method, and is distributed on the surface of the glassy carbon electrode in a layered mode under an self-assembly effect of nano particles so as to form a uniform membrane structure, and the catalysis and a favorable electronic transmitting effect on the o-phenylenediamine are realized. The o-phenylenediamine sensor manufactured according to the invention can be used for the rapid and accurate determination of the o-phenylenediamine, expresses reliably and stably in an analysis experiment of commercially available samples, and has the favorable characteristics of low manufacturing cost, long service life, favorable reproducibility and the like.

Description

A kind of electrochemical sensor of high sensitivity measuring o-phenylenediamine and assay method thereof
Technical field
The present invention relates to a kind of perovskite composite nano materials LaNiTiO that utilizes 3-Fe 3o 4modified glassy carbon electrode (GCE) is measured method, metal nanometer material technology and the electrochemical analysis detection technique field of o-phenylenediamine (o-phenylenediamine).
Background technology
Calcium-titanium ore type nano material has several functions character, the characteristics such as its catalytic oxidation character, electronics hereditary property and film forming make calcium-titanium ore type nano material in the research of electrochemical field by extensive concern, about the fundamental research of these character, also the structure for the electrochemical sensor based on calcium-titanium ore type nano material provides support; On the other hand, because Electrochemical Detection means are quick, sensitive, synthetic calcium-titanium ore type nano material economy, durable, makes calcium-titanium ore type nano material have very large potentiality in practical application and the popularization of electrochemical sensor direction.
O-phenylenediamine is a kind of conventional chemical components, is extensively present in the chemical products such as pesticide, film development agent, rubber antioxidants, surfactant and coloring agent.Meanwhile, o-phenylenediamine is as a kind of carcinogenic, teratogenesis composition, very important to its management and monitoring.To containing, maybe may to contain the management of product of o-phenylenediamine very strict in countries in the world, and for example, containing the product of phenyl amines, wherein the additive capacity of o-phenylenediamine need mark separately and must not surpass prescribed dose; The product of direct cutaneous contact class must not detect o-phenylenediamine as hair dye etc.In addition, because the problems such as environmental pollution, food security become increasingly conspicuous, people deepen day by day to healthy demand, more comprehensively, more strict supervision is urgently put into effect, and meets these, must need more reliably, the support of new technology more easily.
Along with the progress of modern technologies, for the detection technique of o-phenylenediamine, also at development, the detection method for o-phenylenediamine is mainly spectrum and chromatographic technique in early days, but along with the previous method of the raising of testing requirement has been difficult to be competent at.For the detection technique of o-phenylenediamine, aspect accuracy, sensitivity, make larger improvement in recent years, but owing to detecting complex operation step or relying on complex experiment equipment, be difficult to meet the requirement of Site Detection, express-analysis.The electrochemical sensor building based on calcium-titanium ore type nano material, on the one hand because its response is fast, highly sensitive and easy and simple to handle, can make up the deficiency of above-mentioned detection means preferably; On the other hand, due to the special structure of calcium-titanium ore type nano material and performance, be convenient to store, cost is low, more conventional biological enzyme composition is more economical and stable, for the development of downstream sensor product provides good platform.
Summary of the invention
The object of this invention is to provide a kind of new calcium titanium ore composite nano materials LaNiTiO 3-Fe 3o 4the method of modified glassy carbon electrode and as the using method of o-phenylenediamine sensor.
A kind of new calcium titanium ore composite nano materials LaNiTiO 3-Fe 3o 4the preparation method who builds electrochemical sensor, is characterized in that having following process and step:
A. the pre-service of glass-carbon electrode: the H that first glassy carbon electrodes is used to 0.5M 2sO 4soak half an hour, then rinse well; The glass-carbon electrode of rinsing well is ground 5 minutes with 5000 object sand paper, then with the alumina powder of 1mm, 0.3mm, 0.05mm, on chamois leather, grind 5 minutes respectively, make the glass-carbon electrode after polishing be smooth minute surface, then use successively the H of absolute ethyl alcohol, 0.5M 2sO 4with each ultrasonic cleaning of ultrapure water 5 minutes, cleaned standby seam;
B. LaNiTiO 3-Fe 3o 4the preparation of modified glassy carbon electrode: first configure certain density LaNiTiO with ultrapure water 3-Fe 3o 4suspension, optimum concentration is 0.10mg/mL, at room temperature sonic oscillation is 4 hours; Then by the glass-carbon electrode of milled H2SO4 (0.5M) in adopt cyclic voltammetry to activate (1V ~ 1V) to it, and with ultrapure water, electrode is cleaned; Then by finely dispersed LaNiTiO 3-Fe 3o 4(15 μ L) drips and to be coated on the glass-carbon electrode surface of handling well, is positioned under infrared lamp, to dry that after 15 minutes, to be cooled to room temperature stand-by; This be by LaNiTiO 3-Fe 3o 4the electrochemical sensor LaNiTiO modifying 3-Fe 3o 4/ GCE.
A kind of as o-phenylenediamine electrochemical sensor mensuration and the using method in detecting o-phenylenediamine process, above-mentioned modified stand-by electrode can be directly used in the electrochemical gaging of o-phenylenediamine, and its using method and assay method are as follows: by above-mentioned modified electrode LaNiTiO 3-Fe 3o 4/ GCE as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, form three-electrode system; While measuring o-phenylenediamine, three-electrode system is placed in to the 0.1 M NaOH solution of 10 mL, in working electrode anode potential, apply the voltage of 0.3V, apply-0.3V of negative electrode voltage, record square wave volt-ampere pulse curve, when background current reaches after stable state, with microsyringe, in 0.1 M NaOH solution, add the accurate solution of o-phenylenediamine; Under different o-phenylenediamine solution concentration, record the peak current response of sensor to o-phenylenediamine, and within the scope of concentration 1 μ M～7 mM, obtain the linear relationship curve of electric current and o-phenylenediamine concentration, its linearly dependent coefficient is 0.9975, utilizes calibration curve method to carry out analyzing and testing to o-phenylenediamine sample.
Advantage and disadvantage of the present invention is as described below:
The present invention has utilized electrochemical catalysis character, electronics hereditary property and the film-forming quality of Ca-Ti ore type composite nano materials, o-phenylenediamine is carried out to catalytic oxidation applying under the condition of certain potentials, and more existing o-phenylenediamine detection means is highly sensitive; The commercially available sample of complicated component is had to good o-phenylenediamine selectivity; Halide ion, copper ion, benzoate, phthaladehyde are had to good anti-interference; Meanwhile, the structure of sensor and testing process are more economical, more convenient, reliable to the detection of sample.
 
Accompanying drawing explanation
Fig. 1 is under top condition, adds the square-wave pulse volt-ampere curve figure of the o-phenylenediamine standard solution of variable concentrations.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
Preparation method and the step of the modified glassy carbon electrode in the present embodiment are as follows:
(1) pre-service of glass-carbon electrode: the H that first glassy carbon electrodes is used to 0.5M 2sO 4soak half an hour, then rinse well; The glass-carbon electrode of rinsing well is ground 5 minutes with 5000 object sand paper, then with the alumina powder of 1mm, 0.3mm, 0.05mm, on chamois leather, grind 5 minutes respectively, make the glass-carbon electrode after polishing be smooth minute surface, then use successively the H of absolute ethyl alcohol, 0.5M 2sO 4with each ultrasonic cleaning of ultrapure water 5 minutes, cleaned standby seam;
(2) LaNiTiO 3-Fe 3o 4the preparation of modified glassy carbon electrode: first configure certain density LaNiTiO with ultrapure water 3-Fe 3o 4suspension, optimum concentration is 0.10mg/mL, at room temperature sonic oscillation is 4 hours; Then by the glass-carbon electrode of milled H2SO4 (0.5M) in adopt cyclic voltammetry to activate (1V ~ 1V) to it, and with ultrapure water, electrode is cleaned; Then by finely dispersed LaNiTiO 3-Fe 3o 4(15 μ L) drips and to be coated on the glass-carbon electrode surface of handling well, is positioned under infrared lamp, to dry that after 15 minutes, to be cooled to room temperature stand-by.
(3) LaNiTiO 3-Fe 3o 4the using method of modified glassy carbon electrode:
The method that this modified electrode is measured o-phenylenediamine is as follows: by above-mentioned modified electrode LaNiTiO 3-Fe 3o 4/ GCE as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, form three-electrode system; While measuring o-phenylenediamine, three-electrode system is placed in to the 0.1 M NaOH solution of 10 mL, in working electrode anode potential, apply the voltage of 0.3V, apply-0.3V of negative electrode voltage, record square wave volt-ampere pulse curve, when background current reaches after stable state, with microsyringe, in 0.1 M NaOH solution, add the accurate solution of o-phenylenediamine; Under different o-phenylenediamine solution concentration, record the peak current response of sensor to o-phenylenediamine, and within the scope of concentration 1 μ M～7 mM, obtain the linear relationship curve of electric current and o-phenylenediamine concentration, its linearly dependent coefficient is 0.9965, utilizes calibration curve method to carry out analyzing and testing to o-phenylenediamine sample.
Electrochemical gaging o-phenylenediamine:
Adopt o-phenylenediamine concentration 0.0 (a), 1.0 * 10 -6(b), 5.0 * 10 -6(c), 1.0 * 10 -5(d), 2.0 * 10 -5(e), 5.0 * 10 -5(f), 1.0 * 10 -4(g), 2.0 * 10 -4(h), 4.0 * 10 -4(i), 6.0 * 10 -4(j), 8.0 * 10 -4(k), 1.0 * 10 -3(l), 1.5 * 10 -3(m), 3.0 * 10 -3(n), 4.0 * 10 -3(o), 5.0 * 10 -3(p), 6.0 * 10 -3(q), 7.0 * 10 -3(r) ML -1.
Test condition: with LaNiTiO 3-Fe 3o 4modified electrode is working electrode, take saturated calomel electrode as contrast electrode, take platinum electrode as electrode is formed to three-electrode system; Electrolytic solution is 0.1M sodium hydroxide solution.Adopt cyclic voltammetry, apply-0.3V is to the current potential of+0.3V, and surface sweeping speed 100mV/s, scans 10 circles with stabilized electrodes, carries out afterwards square wave volt-ampere impulse method and measures.
Referring to accompanying drawing, the o-phenylenediamine that Fig. 1 is variable concentrations is at LaNiTiO 3-Fe 3o 4square wave volt-ampere pulse curve on modified electrode.
As seen from the figure, along with the increase of o-phenylenediamine concentration, oxidation peak current increases gradually, obtains the linear correlation curve of o-phenylenediamine concentration and current peak i(μ A)=1.357+15.64 c(mM), R=0.9975.
O-phenylenediamine sensor prepared by the inventive method has good selectivity, stability and anti-interference.In the mensuration of the commercially available sample of complicated component, shown good selectivity; Room temperature storage can keep 98.1% of initial response after 30 days, and the halide ions of 10 times, copper ion, benzoate, phthaladehyde are had to good anti-interference; Lowest detectable limit reaches 0.15 μ M.

Claims (2)

1. an electrochemical sensor for high sensitivity measuring o-phenylenediamine, is characterized in that having following preparation process and step:
First prepare perovskite composite nano materials LaNiTiO 3-Fe 3o 4modified glassy carbon electrode:
A. the pre-service of glass-carbon electrode (GCE): the H that first glassy carbon electrodes (GCE) is used to 0.5M 2sO 4soak half an hour, then rinse well; The glass-carbon electrode of rinsing well is ground 5 minutes with 5000 object sand paper, then with the alumina powder of 1mm, 0.3mm, 0.05mm, on chamois leather, grind 5 minutes respectively, make the glass-carbon electrode after polishing be smooth minute surface, then use successively the H of absolute ethyl alcohol, 0.5M 2sO 4with each ultrasonic cleaning of ultrapure water 5 minutes, cleaned standby seam;
B. LaNiTiO 3-Fe 3o 4the preparation of modified glassy carbon electrode (GCE): first configure certain density LaNiTiO with ultrapure water 3-Fe 3o 4suspension, optimum concentration is 0.10mg/mL, at room temperature sonic oscillation is 4 hours; Then by the glass-carbon electrode of milled H 2sO 4(0.5M) in, adopt cyclic voltammetry to activate (0.3V ~+0.3V) to it, and with ultrapure water, electrode is cleaned; Then by finely dispersed LaNiTiO 3-Fe 3o 4(15 μ L) drips and is coated on the glass-carbon electrode surface of handling well, is positioned under infrared lamp and dries 15 minutes, is cooled to room temperature, obtains by LaNiTiO 3-Fe 3o 4the electrochemical sensor LaNiTiO modifying 3-Fe 3o 4/ GCE.
One kind as o-phenylenediamine electrochemical sensor mensuration and the using method in detecting o-phenylenediamine process, above-mentioned modified stand-by electrode can be directly used in the electrochemical gaging of o-phenylenediamine, and its using method and assay method are as follows: by above-mentioned modified electrode LaNiTiO 3-Fe 3o 4/ GCE as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, form three-electrode system; While measuring o-phenylenediamine, three-electrode system is placed in to the 0.1 M NaOH solution of 10 mL, in working electrode anode potential, apply the voltage of 0.3V, apply-0.3V of negative electrode voltage, record square wave volt-ampere pulse curve, when background current reaches after stable state, with microsyringe, in 0.1 M NaOH solution, add the accurate solution of o-phenylenediamine; Under different o-phenylenediamine solution concentration, record the peak current response of sensor to o-phenylenediamine, and within the scope of concentration 1 μ M～7 mM, obtain the linear relationship curve of electric current and o-phenylenediamine concentration, its linearly dependent coefficient is 0.9975, utilizes calibration curve method to carry out analyzing and testing to o-phenylenediamine sample.
CN201310471935.3A 2013-10-11 2013-10-11 A kind of electrochemical sensor of high sensitivity measuring o-phenylenediamine and assay method thereof Expired - Fee Related CN103543188B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105203521A (en) * 2015-10-22 2015-12-30 南华大学 O-phenylenediamine detection method based on nano-interface energy transferring
CN105806920A (en) * 2016-03-16 2016-07-27 济南大学 Preparation method of chlordimeform non-enzymatic sensor constructed on basis of molybdenum sulfide composite material and application
CN110542712A (en) * 2019-09-20 2019-12-06 肇庆学院 preparation method of electrochemical sensor for detecting copper ions with high sensitivity

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
M. CERNEA等: "Preparation by sol–gel and solid state reaction methods and properties investigation of double perovskite Sr2FeMoO6", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》, vol. 33, 20 April 2013 (2013-04-20), pages 2483 - 2490 *
YULONG WANG等: "Preparation of perovskite-type composite oxide LaNi0.5Ti0.5O3–NiFe2O4 and its application in glucose biosensor", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》, vol. 642, 4 February 2010 (2010-02-04), pages 35 - 40 *
嵇正平等: "流动注射化学发光法测定邻苯二胺的研究", 《分析化学》, vol. 37, 31 October 2009 (2009-10-31), pages 139 *
徐彦红: "金属复合氧化物纳米材料的制备及其在电化学传感器中的应用研究", 《中国博士学位论文全文数据库》, 31 December 2011 (2011-12-31), pages 108 - 135 *
李俊华等: "TiO2 /HAP /MWCNT 纳米复合薄膜修饰电极伏安法测定", 《分析化学》, vol. 39, no. 12, 31 December 2011 (2011-12-31), pages 1864 - 1870 *
陈国树等: "环境水样中邻苯二胺测定的阻抑动力学光度法", 《分析测试学报》, vol. 19, no. 6, 30 November 2000 (2000-11-30), pages 21 - 23 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105203521A (en) * 2015-10-22 2015-12-30 南华大学 O-phenylenediamine detection method based on nano-interface energy transferring
CN105203521B (en) * 2015-10-22 2017-11-24 南华大学 A kind of o-phenylenediamine detection method based on nano-interface energy transfer
CN105806920A (en) * 2016-03-16 2016-07-27 济南大学 Preparation method of chlordimeform non-enzymatic sensor constructed on basis of molybdenum sulfide composite material and application
CN105806920B (en) * 2016-03-16 2018-09-14 济南大学 A kind of preparation method and application of the Spanon without enzyme sensor based on vulcanization molybdenum composite material structure
CN110542712A (en) * 2019-09-20 2019-12-06 肇庆学院 preparation method of electrochemical sensor for detecting copper ions with high sensitivity
CN110542712B (en) * 2019-09-20 2020-04-24 肇庆学院 Preparation method of electrochemical sensor for detecting copper ions with high sensitivity

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