CN105806916A - High-sensitivity cadmium ion electrode based on polypyrrole and preparation method thereof - Google Patents
High-sensitivity cadmium ion electrode based on polypyrrole and preparation method thereof Download PDFInfo
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- CN105806916A CN105806916A CN201610336711.5A CN201610336711A CN105806916A CN 105806916 A CN105806916 A CN 105806916A CN 201610336711 A CN201610336711 A CN 201610336711A CN 105806916 A CN105806916 A CN 105806916A
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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Abstract
The invention provides a high-sensitivity cadmium ion electrode based on polypyrrole.The high-sensitivity cadmium ion electrode sequentially comprises a metal wire, a conductive polypyrrole film, a cadmium ion sensitive film and a glass tube from inside to outside.The cadmium ion sensitive film comprises a pyrrole-methyl methacrylate copolymer.The methyl methacrylate and pyrrole copolymer is used as the film forming material of the sensitive film to replace PVC in the prior art, and has the good compatibility with conductive polypyrrole on the adjacent layer, interlayer acting force is increased, and interlayer signal transmission loss is reduced, so that the ion electrode sensitivity is further enhanced, the electrode detection concentration is as low as 2*10<-8> mol/L; meanwhile, the number of adsorption points of the copolymer is increased, the ion adsorption ability of the copolymer is improved, and the cadmium ion detection range is enlarged.
Description
Technical field
The invention belongs to electrochemical analysis techniques field, be specifically related to a kind of Cadmium ion-selective electrode, particularly relate to a kind of high sensitivity Cadmium ion-selective electrode based on polypyrrole and preparation method thereof.
Background technology
Ion selective electrode (ISE) is Applied Electrochemistry principle and technology, in utilizing chemical cell, the composition of analyzed solution and the relation of content and its electrochemical properties are to carry out chemical analysis, and it has the useful tool of the advantages such as simple to operate, response rapid, zero maintenance cost, safety non-toxic and is widely used in the field such as environment, chemistry as a class.
Conducting polymer enjoys researcher to pay close attention to its special optical property, electric property, redox characteristic etc..Its invention is not only various structural materials and improves performance and impart New function, and the structure for various electronic components with device provides novel substance with performance optimization.Among these conductive polymer applications in ISE Copper diethlydithiocarbamate be exactly typical illustration.This mainly has benefited from the plastic processability that conducting polymer is more superior than Conductive inorganic thing, makes the integrated of material and is assembled into possibility.They can be molded directly within base electrode with electrochemical polymerization, or casts on base electrode by chemical oxidising polymerisation product, reaches molding the purpose of modification basic electrode.The more important thing is, conducting polymer has the macromolecular chain of conjugated structure, there is the electric conductivity of electronic conduction and ion simultaneously, therefore, can be as ion-electron transducer, be highly suitable as in solid electrode ion-electron conversion intermediate layer, for development be prone to miniaturization, provide material base without internal-filling liquid, durable solid-state ISE.
Cadmium pollution is widely present in the waste water in mine, smelting ferrum, incinerating waste material process, cadmium plating industry, chemical industry and Production of manure industry, enters in soil and rivers and is difficult to natural degradation, easily causes cadmium pollution problem in various degree.The toxicity of cadmium is bigger, serious to harm by air and the food of cadmium pollution, respiratory tract can be produced by cadmium to stimulate, long-term exposure can cause anosmia, gingiva macula lutea or gradually become Huang circle, cadmium compound is difficult to by intestinal absorption, but liver can be lodged in or kidney works the mischief through breathing by body absorption, especially with the most obvious to kidney damage.Solid electrode is widely used in the mensuration of cadmium ion content in sewage, there is efficient, accurate, easy to operate advantage, but current existing solid electrode sensitivity is limited, when measuring low concentration cadmium ion, difficulty is higher, and therefore a kind of high sensitivity cadmium ion solid electrode of exploitation becomes problem demanding prompt solution.
Summary of the invention
It is an object of the invention to provide a kind of high sensitivity Cadmium ion-selective electrode based on polypyridine, it is possible to detect rapidly concentration as little as 2 × 10-8The cadmium ion of mol/L.
The present invention solves the technical scheme that technical problem used:
A kind of high sensitivity Cadmium ion-selective electrode based on polypyrrole, includes the most successively: tinsel, electric polypyrrole film, cadmium ion sensitive membrane and glass tubing, comprises pyrroles-methylmethacrylate copolymer in described cadmium ion sensitive membrane.Pyrroles-methyl methacrylate, as the sensitive membrane of main component, has the preferable compatibility with electric polypyrrole, is conducive to increasing interlaminar action power, reduces the transmission loss of interlayer signal, thus further enhances the sensitivity of ion electrode；Use pyrroles and methyl methacrylate copolymer, strand introduces polar group, improves dissolubility and the chain pliability of polypyrrole, increase the adsorption site of copolymer simultaneously, improve its ion adsorption capacity, expand the detection range of cadmium ion.
As preferably, described material wiry is silver, gold or platinum.
Invention also provides a kind of method preparing high sensitivity Cadmium ion-selective electrode based on polypyrrole, comprise the steps:
(1) wire surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 15 ~ 30 minutes, then rinse well with deionized water, and be dried；
(2) by uniform with 10 ~ 15% combined for pyrroles, the tinsel cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.8V potential range, thus plate one layer of electric polypyrrole film in wire surface, wherein tinsel is that working electrode, saturated calomel electrode and platinum electrode make reference electrode and respectively to electrode；
(3) lower 10-18 weight portion pyrroles-methylmethacrylate copolymer, 3-8 weight portion cadmium ion carrier III, 15-20 weight portion 2-Nitrobenzol octyl ether, 1-3 weight portion four (4-chlorphenyl) potassium borate and 56-64 pbw acetone mix homogeneously are obtained anion screened film solution；
(4) electrode that step (2) gained is coated with polypyrrole dips step (3) gained anion screened film solution, fall to insert on foam, after 58 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates cadmium ion sensitive membrane；
(5) glass tubing is coated on outside cadmium ion sensitive membrane, 0.5-1 centimetre, described glass tubing distance sensitive film lower end.
As preferably, pyrroles described in step (2) is 1:0.8 ~ 1 with the mass ratio of 10 ~ 15% aqueous hydrochloric acid solutions.
Polypyrrole, due to its chain rigidity and interchain strong interaction, makes its solubility extreme difference, the most insoluble in the organic solvent that major part is conventional.And use methyl methacrylate and pyrroles's copolymerization to prepare modified polypyrrole, owing to its strand introducing polar group methyl methacrylate, considerably increase the strand pliability of copolymer, it is made to be dissolved in lower boiling acetone, thus avoid step (4) drying course produces destruction because temperature is too high to cadmium ion carrier III structure, maintain the high sensitivity of sensitive membrane.
The invention have the benefit that
1, the present invention uses methyl methacrylate and co-pyrrole copolymer as the filmogen of sensitive membrane, substitute PVC of the prior art, with the electric polypyrrole of adjacent layer, there is the preferable compatibility, increase interlaminar action power, reduce the transmission loss of interlayer signal, thus further enhance the sensitivity of ion electrode so that electrode detection concentration limit as little as 2 × 10-8mol/L；Increase the adsorption site of copolymer simultaneously, improve its ion adsorption capacity, expand the detection range of cadmium ion.
2, methyl methacrylate polypyrrole compared with co-pyrrole copolymer has more preferable dissolubility in organic solvent, i.e. dissolve under room temperature in low boiling acetone, thus avoid step (4) drying course produces destruction because temperature is too high to cadmium ion carrier III structure, maintain the high sensitivity of sensitive membrane.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
(1) filamentary silver surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 15 minutes, then rinse well with deionized water, and be dried；
(2) by uniform with 8g 15% combined for 10g pyrroles, the filamentary silver cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.8V potential range, continuously scanning 10 circulation, thus at one layer of electric polypyrrole film of filamentary silver plated surface, wherein filamentary silver is that working electrode, saturated calomel electrode and platinum electrode make reference electrode and respectively to electrode；
(3) 10g pyrroles-methylmethacrylate copolymer, 5g cadmium ion carrier III, 20g 2-Nitrobenzol octyl ether, 1g tetra-(4-chlorphenyl) potassium borate and 64g acetone mix homogeneously are obtained anion screened film solution；
(4) electrode that step (2) gained is coated with polypyrrole dips step (3) gained anion screened film solution, fall to insert on foam, after 58 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates cadmium ion sensitive membrane；
(5) glass tubing is coated on outside cadmium ion sensitive membrane, 1 centimetre, described glass tubing distance sensitive film lower end.
Embodiment 2
(1) spun gold surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 20 minutes, then rinse well with deionized water, and be dried；
(2) by uniform with 9g 10% combined for 10g pyrroles, the spun gold cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.8V potential range, continuously scanning 15 circulation, thus at one layer of electric polypyrrole film of spun gold plated surface, wherein spun gold is that working electrode, saturated calomel electrode and platinum electrode make reference electrode and respectively to electrode；
(3) 15g pyrroles-methylmethacrylate copolymer, 3g cadmium ion carrier III, 18g 2-Nitrobenzol octyl ether, 2g tetra-(4-chlorphenyl) potassium borate and 62g acetone mix homogeneously are obtained anion screened film solution；
(4) electrode that step (2) gained is coated with polypyrrole dips step (3) gained anion screened film solution, fall to insert on foam, after 58 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates cadmium ion sensitive membrane；
(5) glass tubing is coated on outside cadmium ion sensitive membrane, 0.5 centimetre, described glass tubing distance sensitive film lower end.
Embodiment 3
(1) filamentary silver surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 30 minutes, then rinse well with deionized water, and be dried；
(2) by uniform with 10g 12% combined for 10g pyrroles, the filamentary silver cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.8V potential range, continuously scanning 20 circulation, thus at one layer of electric polypyrrole film of filamentary silver plated surface, wherein filamentary silver is that working electrode, saturated calomel electrode and platinum electrode make reference electrode and respectively to electrode；
(3) 18g pyrroles-methylmethacrylate copolymer, 8g cadmium ion carrier III, 15g 2-Nitrobenzol octyl ether, 3g tetra-(4-chlorphenyl) potassium borate and 56g acetone mix homogeneously are obtained anion screened film solution；
(4) electrode that step (2) gained is coated with polypyrrole dips step (3) gained anion screened film solution, fall to insert on foam, after 58 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates cadmium ion sensitive membrane；
(5) glass tubing is coated on outside cadmium ion sensitive membrane, 0.8 centimetre, described glass tubing distance sensitive film lower end.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (4)
1. a high sensitivity Cadmium ion-selective electrode based on polypyrrole, it is characterized in that, described Cadmium ion-selective electrode includes the most successively: tinsel, electric polypyrrole film, cadmium ion sensitive membrane and glass tubing, comprises pyrroles-methylmethacrylate copolymer in described cadmium ion sensitive membrane.
2. high sensitivity Cadmium ion-selective electrode based on polypyrrole as claimed in claim 1, it is characterised in that described material wiry is silver, gold or platinum.
3. the method for preparation high sensitivity Cadmium ion-selective electrode based on polypyrrole as claimed in claim 1 or 2, it is characterised in that described preparation method comprises the steps:
(1) wire surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 15 ~ 30 minutes, then rinse well with deionized water, and be dried；
(2) by uniform with 10 ~ 15% combined for pyrroles, the tinsel cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.8V potential range, thus plate one layer of electric polypyrrole film in wire surface, wherein tinsel is that working electrode, saturated calomel electrode and platinum electrode make reference electrode and respectively to electrode；
(3) lower 10-18 weight portion pyrroles-methylmethacrylate copolymer, 3-8 weight portion cadmium ion carrier III, 15-20 weight portion 2-Nitrobenzol octyl ether, 1-3 weight portion four (4-chlorphenyl) potassium borate and 56-64 pbw acetone mix homogeneously are obtained anion screened film solution；
(4) electrode that step (2) gained is coated with polypyrrole dips step (3) gained anion screened film solution, fall to insert on foam, after 58 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates cadmium ion sensitive membrane；
(5) glass tubing is coated on outside cadmium ion sensitive membrane, 0.5-1 centimetre, described glass tubing distance sensitive film lower end.
4. preparation method as claimed in claim 3, it is characterised in that pyrroles described in step (2) is 1:0.8 ~ 1 with the mass ratio of 10 ~ 15% aqueous hydrochloric acid solutions.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610336711.5A CN105806916A (en) | 2016-05-20 | 2016-05-20 | High-sensitivity cadmium ion electrode based on polypyrrole and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106525924A (en) * | 2016-11-15 | 2017-03-22 | 吉林大学 | PVC membrane sensor, and method used for detecting beef taste using PVC membrane sensor |
| RU2688951C1 (en) * | 2018-07-17 | 2019-05-23 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Ion-selective electrode membrane for cadmium ions determination |
Citations (8)
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| EP0056283A1 (en) * | 1981-01-14 | 1982-07-21 | Terumo Corporation | Ion sensor |
| CN101556258A (en) * | 2009-04-03 | 2009-10-14 | 江苏工业学院 | Timolol maleate potentiometric chemical sensor and preparation method thereof |
| CN103154716A (en) * | 2010-07-26 | 2013-06-12 | 赛诺瓦***股份有限公司 | Analyte sensor |
| CN103336044A (en) * | 2013-06-18 | 2013-10-02 | 南京普朗医疗设备有限公司 | All solid-state ion selective electrode and preparation method and application thereof |
| CN103424450A (en) * | 2013-08-26 | 2013-12-04 | 深圳市希莱恒医用电子有限公司 | Ion selective electrode based on conducting polymer film and preparation method thereof |
| WO2015023974A1 (en) * | 2013-08-15 | 2015-02-19 | The Regents Of The University Of California | A multicomponent approach to enhance stability and capacitance in polymer-hybrid supercapacitors |
| CN105021682A (en) * | 2015-07-02 | 2015-11-04 | 浙江大学 | Needle-like chlorine ion sensor and preparation method thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
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2016
- 2016-05-20 CN CN201610336711.5A patent/CN105806916A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0056283A1 (en) * | 1981-01-14 | 1982-07-21 | Terumo Corporation | Ion sensor |
| CN101556258A (en) * | 2009-04-03 | 2009-10-14 | 江苏工业学院 | Timolol maleate potentiometric chemical sensor and preparation method thereof |
| CN103154716A (en) * | 2010-07-26 | 2013-06-12 | 赛诺瓦***股份有限公司 | Analyte sensor |
| CN103336044A (en) * | 2013-06-18 | 2013-10-02 | 南京普朗医疗设备有限公司 | All solid-state ion selective electrode and preparation method and application thereof |
| WO2015023974A1 (en) * | 2013-08-15 | 2015-02-19 | The Regents Of The University Of California | A multicomponent approach to enhance stability and capacitance in polymer-hybrid supercapacitors |
| CN103424450A (en) * | 2013-08-26 | 2013-12-04 | 深圳市希莱恒医用电子有限公司 | Ion selective electrode based on conducting polymer film and preparation method thereof |
| CN105021682A (en) * | 2015-07-02 | 2015-11-04 | 浙江大学 | Needle-like chlorine ion sensor and preparation method thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106525924A (en) * | 2016-11-15 | 2017-03-22 | 吉林大学 | PVC membrane sensor, and method used for detecting beef taste using PVC membrane sensor |
| RU2688951C1 (en) * | 2018-07-17 | 2019-05-23 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Ion-selective electrode membrane for cadmium ions determination |
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