CN106018525A - High sensitivity lead ion electrode based on polypyrrole and preparation method thereof - Google Patents
High sensitivity lead ion electrode based on polypyrrole and preparation method thereof Download PDFInfo
- Publication number
- CN106018525A CN106018525A CN201610336709.8A CN201610336709A CN106018525A CN 106018525 A CN106018525 A CN 106018525A CN 201610336709 A CN201610336709 A CN 201610336709A CN 106018525 A CN106018525 A CN 106018525A
- Authority
- CN
- China
- Prior art keywords
- electrode
- lead ion
- polypyrrole
- high sensitivity
- film
- 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
Classifications
-
- 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
- G01N27/28—Electrolytic cell components
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention provides a high sensitivity lead ion electrode based on polypyrrole and a preparation method thereof. The high sensitivity lead ion electrode based on polypyrrole sequentially comprises a metal wire, a conductive polypyrrole film, a lead ion sensitive film and a glass tube. The lead ion sensitive film comprises a pyrrole-p-hydroxybenzenesulfonic acid copolymer from inside to outside. The pyrrole-p-hydroxybenzenesulfonic acid copolymer is adopted to serve as a film-forming material of the sensitive film and replace PVC in the prior art, has good compatibility with conductive polypyrrole of an adjacent layer, improves interlayer acting force and reduces interlayer signal transmission loss, so that the sensitivity of the ion electrode is further enhanced, and the lower limit of the electrode detection concentration is as low as 108 mol/L. Adsorption points of the copolymer are increased, the ion adsorption capability of the copolymer is improved, and the detection range of lead ions is expanded.
Description
Technical field
The invention belongs to electrochemical analysis techniques field, be specifically related to a kind of lead ion electrode, particularly relate to a kind of high sensitivity lead ion 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.
Lead in environment mainly has the source of two aspects, and one is natural source, refers to the lead that the natural phenomena such as volcano eruption, forest fire is discharged in environment；Two is non-natural source, refers to mankind's activity, mainly the lead discharge of the aspect such as industry and traffic.Lead is the goods and materials that a kind of toxicity is the biggest, and many human organs can be brought harmful effect by lead, particularly to the lung of people, kidney, reproductive system, cardiovascular system.These impacts show as intelligence and decline (especially children for learning aspect being caused obvious problem), injury of kidney, sterile, miscarriage and hypertension, also can cause lead encephalopathy, angina abdominis, polyneuritis, hemolytic anemia etc..Solid electrode is widely used in the mensuration of cadmium ion content in lead water, there is efficient, accurate, easy to operate advantage, but current existing solid electrode sensitivity is limited, when measuring low concentration lead ion, difficulty is higher, and therefore a kind of high sensitivity lead 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 lead ion electrode based on polypyridine, it is possible to detect rapidly concentration as little as 10-8The lead ion of mol/L.
The present invention solves the technical scheme that technical problem used:
A kind of high sensitivity lead ion electrode based on polypyrrole, includes the most successively: tinsel, electric polypyrrole film, lead ion sensitive membrane and glass tubing, comprises pyrroles-p-hydroxybenzenyl sulfonate copolymer in described lead ion sensitive membrane.Pyrroles-p-hydroxybenzenyl sulfonate, 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 p-hydroxybenzenyl sulfonate copolymerization, 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 lead ion.
As preferably, described material wiry is silver, gold or platinum.
Invention also provides a kind of method preparing high sensitivity lead ion 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 0-1.6V 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 12-20 weight portion pyrroles-p-hydroxybenzenyl sulfonate copolymer, 5-8 weight portion lead ion carrier II, 10-16 weight portion 2-Nitrobenzol octyl ether, 3-5 weight portion sodium cetanesulfonate and 58-64 weight portion trichloroethane 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 75 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates lead ion sensitive membrane；
(5) glass tubing is coated on outside lead ion sensitive membrane, 0.5-1 centimetre, described glass tubing distance sensitive film lower end.
As preferably, pyrroles described in step (2) is 1:0.6 ~ 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 p-hydroxybenzenyl sulfonate and pyrroles's copolymerization to prepare modified polypyrrole, owing to its strand introducing polar molecule p-hydroxybenzenyl sulfonate, considerably increase the strand pliability of copolymer, it is made to be dissolved in lower boiling trichloroethane, thus avoid step (4) drying course produces destruction because temperature is too high to lead ion carrier II structure, maintain the high sensitivity of sensitive membrane.
The invention have the benefit that
1, the present invention uses p-hydroxybenzenyl sulfonate 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 10-8mol/L；Increase the adsorption site of copolymer simultaneously, improve its ion adsorption capacity, expand the detection range of lead ion.
2, p-hydroxybenzenyl sulfonate polypyrrole compared with co-pyrrole copolymer has more preferable dissolubility in organic solvent, i.e. dissolve under room temperature in low boiling trichloroethane, thus avoid step (4) drying course produces destruction because temperature is too high to lead ion carrier II 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 6g 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 0-1.6V 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) 15g pyrroles-p-hydroxybenzenyl sulfonate copolymer, 6g lead ion carrier II, 12g 2-Nitrobenzol octyl ether, 3g sodium cetanesulfonate and 64g trichloroethane 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 75 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates lead ion sensitive membrane；
(5) glass tubing is coated on outside lead 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 8g 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 0-1.6V 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) 12g pyrroles-p-hydroxybenzenyl sulfonate copolymer, 5g lead ion carrier II, 16g 2-Nitrobenzol octyl ether, 5g sodium cetanesulfonate and 62g trichloroethane 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 75 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates lead ion sensitive membrane；
(5) glass tubing is coated on outside lead ion sensitive membrane, 0.5 centimetre, described glass tubing distance sensitive film lower end.
Embodiment 3
(1) platinum filament 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 platinum filament cleaned up is placed in one, by electrochemical workstation CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.6V potential range, continuously scanning 20 circulation, thus at one layer of electric polypyrrole film of platinum filament plated surface, wherein platinum filament is that working electrode, saturated calomel electrode and silver electrode make reference electrode and respectively to electrode；
(3) 20g pyrroles-p-hydroxybenzenyl sulfonate copolymer, 8g lead ion carrier II, 10g 2-Nitrobenzol octyl ether, 4g sodium cetanesulfonate and 58g trichloroethane 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 75 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates lead ion sensitive membrane；
(5) glass tubing is coated on outside lead 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 lead ion electrode based on polypyrrole, it is characterized in that, described lead ion electrode includes the most successively: tinsel, electric polypyrrole film, lead ion sensitive membrane and glass tubing, comprises pyrroles-p-hydroxybenzenyl sulfonate copolymer in described lead ion sensitive membrane.
2. high sensitivity lead ion 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 lead ion 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 0-1.6V 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 12-20 weight portion pyrroles-p-hydroxybenzenyl sulfonate copolymer, 5-8 weight portion lead ion carrier II, 10-16 weight portion 2-Nitrobenzol octyl ether, 3-5 weight portion sodium cetanesulfonate and 58-64 weight portion trichloroethane 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 75 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates lead ion sensitive membrane；
(5) glass tubing is coated on outside lead 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 1:0.6 ~ 1 with the mass ratio of 10 ~ 15% aqueous hydrochloric acid solutions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610336709.8A CN106018525A (en) | 2016-05-20 | 2016-05-20 | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610336709.8A CN106018525A (en) | 2016-05-20 | 2016-05-20 | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106018525A true CN106018525A (en) | 2016-10-12 |
Family
ID=57095595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610336709.8A Pending CN106018525A (en) | 2016-05-20 | 2016-05-20 | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106018525A (en) |
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 |
| CN108287186A (en) * | 2017-01-09 | 2018-07-17 | 天津大学 | A kind of device of detection lead ion |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852761A (en) * | 2010-05-18 | 2010-10-06 | 浙江大学 | All-solid sodium ion selective electrode and preparation method thereof |
| CN101858882A (en) * | 2010-03-17 | 2010-10-13 | 江南大学 | Nitrate ion selective electrode based on polypyrrole film and preparation method thereof |
| CN102156157A (en) * | 2011-01-10 | 2011-08-17 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
| CN103063724A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid carbonate ion electrode based on conductive polyaniline and preparing method thereof |
| 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 |
| WO2015042971A1 (en) * | 2013-09-30 | 2015-04-02 | Tongji University | Lead ion sensors, methods of making and uses thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
-
2016
- 2016-05-20 CN CN201610336709.8A patent/CN106018525A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858882A (en) * | 2010-03-17 | 2010-10-13 | 江南大学 | Nitrate ion selective electrode based on polypyrrole film and preparation method thereof |
| CN101852761A (en) * | 2010-05-18 | 2010-10-06 | 浙江大学 | All-solid sodium ion selective electrode and preparation method thereof |
| CN102156157A (en) * | 2011-01-10 | 2011-08-17 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
| CN103063724A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid carbonate ion electrode based on conductive polyaniline and preparing method thereof |
| 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 |
| WO2015042971A1 (en) * | 2013-09-30 | 2015-04-02 | Tongji University | Lead ion sensors, methods of making and uses 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 |
| CN108287186A (en) * | 2017-01-09 | 2018-07-17 | 天津大学 | A kind of device of detection lead ion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Sensors based on conductive polymers and their composites: a review | |
| CN101392060B (en) | Quaternized polybenzimidazoles and preparation method thereof | |
| CN101871912B (en) | Full-solid potassium ion sensor and preparation method thereof | |
| Wei et al. | Highly stretchable, fast self‐healing, responsive conductive hydrogels for supercapacitor electrode and motion sensor | |
| CN100374492C (en) | Method for preparing chitose proton exchange membrance for fuel cell | |
| CN101844042A (en) | Preparation method of anion-exchange membranes based on ionic liquid | |
| CN105694077A (en) | Anion exchange membrane containing pyridine skeleton as well as preparation method and application of anion exchange membrane | |
| CN105406091B (en) | A kind of preparation method of Kynoar heteropoly acid chitosan compound proton exchange membrane | |
| CN106548877A (en) | Carbon nano pipe array/polyaniline/ceria composite electrode and its preparation method and application | |
| CN103456508B (en) | Method for manufacturing graphene composite electrode | |
| CN106018525A (en) | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof | |
| CN101891899A (en) | Ionic liquid doped heterocyclic polyarylether or sulfonate thereof for high-temperature and low-humidity ionic membrane and preparation method thereof | |
| CN104914150A (en) | Graphene/polyaniline composite membrane based pH detecting electrode | |
| CN108219086A (en) | One kind is based on fullerene anion exchange membrane and preparation method thereof | |
| Li et al. | Robust conducting gel electrolytes for efficient quasi-solid-state dye-sensitized solar cells | |
| CN112098485B (en) | Photoelectrochemical aptamer sensor based on sensing separation strategy and preparation method and application thereof | |
| Song et al. | Imidazolium-functionalized anion exchange polymer containing fluorine group for fuel cell application | |
| CN101445618B (en) | A preparation method of self-supporting poly (3, 4- ethylenedioxythiophene) porous membrane | |
| Hazra et al. | Organic mixed ion-electron conductivity in polymer hybrid systems | |
| CN105806916A (en) | High-sensitivity cadmium ion electrode based on polypyrrole and preparation method thereof | |
| Liang et al. | Improved performance of carbon‐based supercapacitors with sulfonated poly (ether ether ketone)/poly (vinyl alcohol) composite membranes as separators | |
| CN105566884A (en) | Anion-exchange membrane containing xanthene structure and preparation method and application of anion-exchange membrane | |
| CN106654328A (en) | Fluorine-containing ion exchange membrane for fuel cell and preparation method of fluorine-containing ion exchange membrane | |
| He et al. | Organic Electrochemical Transistor Based on Hydrophobic Polymer Tuned by Ionic Gels | |
| CN107129592B (en) | A kind of cellulosic polymer dielectric film and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20190409 |
|
| AD01 | Patent right deemed abandoned |