CN106053582A - Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof - Google Patents
Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof Download PDFInfo
- Publication number
- CN106053582A CN106053582A CN201610336712.XA CN201610336712A CN106053582A CN 106053582 A CN106053582 A CN 106053582A CN 201610336712 A CN201610336712 A CN 201610336712A CN 106053582 A CN106053582 A CN 106053582A
- Authority
- CN
- China
- Prior art keywords
- electrode
- mercury ion
- polyaniline
- aniline
- sensitive membrane
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a polyaniline based mercury ion electrode, which comprises the following components from inner to outer in sequence: a metal wire, a conductive polyaniline membrane, a mercury ion sensitive membrane, and a glass tube. The mercury ion sensitive membrane comprises an aniline-sulfosalicylic acid copolymer. The aniline-sulfosalicylic acid copolymer is taken as the film forming material of a sensitive membrane and is used to replace PVC used in the prior art. The compatibility between the aniline-sulfosalicylic acid copolymer and conductive polyaniline in the neighbored layer is good, the interlayer acting force is enhanced, the interlayer signal transmission loss is reduced, the ion electrode sensitivity is further enhanced, at the same time, the adsorption points of the copolymer are increased, the ion adsorption performance of the copolymer is strengthened therefore, the detection range of mercury ion is enlarged; compared with polyaniline, the aniline-sulfosalicylic acid copolymer is better dissolved in an organic solvent, can be dissolved into tetrahydrofuran with a low boiling point at a room temperature, thus the V structure of the mercury ion carrier will not be destroyed during the drying process due to high temperature, and the high sensitivity of the sensitive membrane is maintained.
Description
Technical field
The invention belongs to electrochemical analysis techniques field, be specifically related to a kind of mercury ion electrode, particularly relate to a kind of based on
High sensitivity mercury ion electrode of polyaniline and preparation method thereof.
Background technology
Ion selective electrode (ISE) is Applied Electrochemistry principle and technology, the group of analyzed solution in utilizing chemical cell
Become and the relation of content and its electrochemical properties carry out chemical analysis, its as a class have simple to operate, response rapidly, zero
The useful tool of the advantage such as maintenance cost, safety non-toxic and be widely used in the field such as environment, chemistry.
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 is the structure of various electronic component and device
Build and provide 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 be assembled into can
Energy.They can be molded directly within base electrode with electrochemical polymerization, or casts in matrix electricity by chemical oxidising polymerisation product
Extremely go up, reach molding the purpose of modification basic electrode.The more important thing is, conducting polymer has big point of conjugated structure
Subchain, has the electric conductivity of electronic conduction and ion simultaneously, therefore, it can as ion-electron transducer, is especially suitable for using
Make in solid electrode ion-electron conversion intermediate layer, for development be prone to miniaturization, without internal-filling liquid, durable
Solid-state ISE provides material base.
Mercury ion, as a heavy metal species, derives from chlor-alkali industry, plastic industry, electronics industry, amalgamation gold metallurgy and mercury fulminate
The waste water of discharge such as produce, it has, and toxicity is big, bioconcentration strong, can not the complicated feature of natural degradation and source, to life
State environment causes serious harm.Solid electrode is widely used in the mensuration of mercury ion content in sewage, has efficient, accurate
Really, easy to operate advantage, but current existing solid electrode sensitivity is limited, when measuring Low Concentration Mercury ion, difficulty is relatively
Height, therefore a kind of high sensitivity mercury 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 mercury ion electrode based on polyaniline, it is possible to detect rapidly dense
Degree as little as 10-8The mercury ion of mol/L.
The present invention solves the technical scheme that technical problem used:
A kind of high sensitivity mercury ion electrode based on polyaniline, includes the most successively: tinsel, Polyaniline Film,
Mercury ion sensitive membrane and glass tubing, described mercury ion sensitive membrane includes aniline-sulfosalisylic acid copolymer.Aniline-sulfo group water
Poplar acid copolymer, as the sensitive membrane of main component, has the preferable compatibility with electrically conductive polyaniline, increases interlaminar action power, subtracts
Few interlayer signal transmission loss, thus further enhance the sensitivity of ion electrode；Use aniline and sulfosalicylic acid copolymerization,
Introducing the sulfonic acid group with chelating function and ion exchanging function on strand, the dissolubility and the chain that improve polyaniline are pliable and tough
Property, increase the adsorption site of copolymer simultaneously, improve its ion adsorption capacity, expand the detection range of mercury ion.
As preferably, described material wiry is silver, gold or platinum.
Invention also provides a kind of method preparing high sensitivity mercury ion electrode based on polyaniline, including as follows
Step:
(1) wire surface is polished smooth, after being placed in 15% aqueous hydrochloric acid solution ultrasonic cleaning 15 ~ 30 minutes, then spend from
Sub-water is rinsed well, and is dried；
(2) by uniform to aniline and 10 ~ 15% combined, the tinsel cleaned up is placed in one, by electrification
Learn work station CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.6V potential range, thus
Plating one layer of Polyaniline Film in wire surface, wherein tinsel is working electrode, and saturated calomel electrode and platinum electrode are respectively
Make reference electrode and to electrode；
(3) by lower 12-15 weight portion aniline-sulfosalisylic acid copolymer, 1-3 parts by weight of mercury ionophore V, 20-25 weight
Part 2-Nitrobenzol octyl ether, 0.5-1.5 weight portion four (4-chlorphenyl) potassium borate and 57-66 weight portion oxolane mix homogeneously obtain
To anion screened film solution；
(4) electrode that step (2) gained is coated with polyaniline dips step (3) gained anion screened film solution, is inserted in
On foam plastics, after 65 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates mercury ion sensitive membrane.
(5) glass tubing is coated on outside mercury ion sensitive membrane, 0.5-1 centimetre, described glass tubing distance sensitive film lower end,
The end and the portion sides that make solid electrode all can play detection effect.
As preferably, described in step (2), the mass ratio of aniline and 10 ~ 15% aqueous hydrochloric acid solutions is 1:0.5 ~ 0.8.
Polyaniline, due to its chain rigidity and interchain strong interaction, makes its solubility extreme difference, in conventional the having of major part
In machine solvent the most insoluble, be only partially soluble in DMF and N-Methyl pyrrolidone, and the boiling of both solvents
Point is the highest, the most volatile, if it is too high to dry temperature, then can destroy mercury ion carrier V structure, thus affect its to hydrargyrum from
The absorbability of son.And use the polyaniline of sulfosalicylic acid modification, introduce polar group hydroxy-acid group owing to its strand is raw
And sulfonic acid group, considerably increase the strand pliability of copolymer so that it is be dissolved in lower boiling oxolane, thus keep away
Exempt from step (4) drying course produces destruction because temperature is too high to mercury ion carrier V structure, maintain the height spirit of sensitive membrane
Quick property.
The invention have the benefit that
1, the present invention uses aniline-sulfosalisylic acid copolymer as the filmogen of sensitive membrane, substitutes of the prior art
PVC, has the preferable compatibility with the electrically conductive polyaniline of adjacent layer, increases interlaminar action power, reduces 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 copolymerization simultaneously
The adsorption site of thing, improves its ion adsorption capacity, expands the detection range of mercury ion.
2, aniline-sulfosalisylic acid copolymer is compared polyaniline and is had more preferable dissolubility in organic solvent, under room temperature
I.e. dissolve in low boiling oxolane, thus avoid mercury ion carrier V is tied because temperature is too high by step (4) drying course
Structure produces and destroys, and maintains 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 to the present invention
It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit
Determine 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 rush with deionized water
Wash clean, and be dried；
(2) 10g aniline is uniform with 5g 15% combined, the filamentary silver cleaned up is placed in one, by electrification
Learn work station 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 Polyaniline Film of filamentary silver plated surface, wherein filamentary silver is working electrode, saturated calomel electrode and
Platinum electrode makees reference electrode and respectively to electrode；
(3) by lower 12g aniline-sulfosalisylic acid copolymer, 2g mercury ion carrier V, 20g 2-Nitrobenzol octyl ether, 0.5g tetra-
(4-chlorphenyl) potassium borate and 65.5g oxolane mix homogeneously obtain anion screened film solution；
(4) electrode that step (2) gained is coated with polyaniline dips step (3) gained anion screened film solution, is inserted in
On foam plastics, after 65 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates mercury ion sensitive membrane；
(5) glass tubing is coated on outside mercury 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 rush with deionized water
Wash clean, and be dried；
(2) 10g aniline is uniform with 8g 10% combined, the filamentary silver cleaned up is placed in one, by electrification
Learn work station 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 Polyaniline Film of spun gold plated surface, wherein spun gold is working electrode, saturated calomel electrode and
Platinum electrode makees reference electrode and respectively to electrode；
(3) by lower 15g aniline-sulfosalisylic acid copolymer, 1g mercury ion carrier V, 22g 2-Nitrobenzol octyl ether, 1g tetra-(4-
Chlorphenyl) potassium borate and 61g oxolane mix homogeneously obtain anion screened film solution；
(4) electrode that step (2) gained is coated with polyaniline dips step (3) gained anion screened film solution, is inserted in
On foam plastics, after 65 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates mercury ion sensitive membrane；
(5) glass tubing is coated on outside mercury 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 rush with deionized water
Wash clean, and be dried；
(2) 10g aniline is uniform with 6g 12% combined, the filamentary silver cleaned up is placed in one, by electrification
Learn work station 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 Polyaniline Film of filamentary silver plated surface, wherein filamentary silver is working electrode, saturated calomel electrode and
Platinum electrode makees reference electrode and respectively to electrode；
(3) by lower 13g aniline-sulfosalisylic acid copolymer, 3g mercury ion carrier V, 25g 2-Nitrobenzol octyl ether, 1.5g tetra-
(4-chlorphenyl) potassium borate and 57.5g oxolane mix homogeneously obtain anion screened film solution；
(4) electrode that step (2) gained is coated with polyaniline dips step (3) gained anion screened film solution, is inserted in
On foam plastics, after 65 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates mercury ion sensitive membrane；
(5) glass tubing is coated on outside mercury 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 essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (4)
1. a high sensitivity mercury ion electrode based on polyaniline, it is characterised in that described mercury ion electrode depends on from inside to outside
Secondary include: tinsel, Polyaniline Film, mercury ion sensitive membrane and glass tubing, described mercury ion sensitive membrane includes aniline-sulphur
Base salicylic acid copolymers.
2. high sensitivity mercury ion electrode based on polyaniline as claimed in claim 1, it is characterised in that described wiry
Material is silver, gold or platinum.
3. the method for preparation high sensitivity mercury ion electrode based on polyaniline 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 spend from
Sub-water is rinsed well, and is dried；
(2) by uniform to aniline and 10 ~ 15% combined, the tinsel cleaned up is placed in one, by electrification
Learn work station CHI660A, with 50mV/S scanning speed, cyclic voltammetry scan activated electrode in 0-1.6V potential range, thus
Plating one layer of Polyaniline Film in wire surface, wherein tinsel is working electrode, and saturated calomel electrode and platinum electrode are respectively
Make reference electrode and to electrode；
(3) by lower 12-15 weight portion aniline-sulfosalisylic acid copolymer, 1-3 parts by weight of mercury ionophore V, 20-25 weight
Part 2-Nitrobenzol octyl ether, 0.5-1.5 weight portion four (4-chlorphenyl) potassium borate and 57-66 weight portion oxolane mix homogeneously obtain
To anion screened film solution；
(4) electrode that step (2) gained is coated with polyaniline dips step (3) gained anion screened film solution, is inserted in
On foam plastics, after 65 DEG C of vacuum drying 24 hours, electrode outermost layer successfully plates mercury ion sensitive membrane；
(5) glass tubing is coated on outside mercury 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 described in step (2), aniline and 10 ~ 15% hydrochloric acid are water-soluble
The mass ratio of liquid is 1:0.5 ~ 0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610336712.XA CN106053582A (en) | 2016-05-20 | 2016-05-20 | Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610336712.XA CN106053582A (en) | 2016-05-20 | 2016-05-20 | Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106053582A true CN106053582A (en) | 2016-10-26 |
Family
ID=57177169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610336712.XA Pending CN106053582A (en) | 2016-05-20 | 2016-05-20 | Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106053582A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110579521A (en) * | 2019-07-31 | 2019-12-17 | 安徽环境科技集团股份有限公司 | Modified electrode for nitrobenzene detection and preparation method and application thereof |
| CN112098497A (en) * | 2020-10-20 | 2020-12-18 | 常州工学院 | Method for electrochemically identifying and detecting aspartic acid enantiomer and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2012067490A1 (en) * | 2010-11-15 | 2012-05-24 | Mimos Berhad | 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 |
| CN103214689A (en) * | 2013-03-20 | 2013-07-24 | 太原理工大学 | Preparation method of ion imprinted polymer film |
| 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 |
-
2016
- 2016-05-20 CN CN201610336712.XA patent/CN106053582A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012067490A1 (en) * | 2010-11-15 | 2012-05-24 | Mimos Berhad | Ion selective electrode |
| 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 |
| CN103214689A (en) * | 2013-03-20 | 2013-07-24 | 太原理工大学 | Preparation method of ion imprinted polymer film |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110579521A (en) * | 2019-07-31 | 2019-12-17 | 安徽环境科技集团股份有限公司 | Modified electrode for nitrobenzene detection and preparation method and application thereof |
| CN110579521B (en) * | 2019-07-31 | 2022-08-30 | 安徽环境科技集团股份有限公司 | Modified electrode for nitrobenzene detection and preparation method and application thereof |
| CN112098497A (en) * | 2020-10-20 | 2020-12-18 | 常州工学院 | Method for electrochemically identifying and detecting aspartic acid enantiomer and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104140545B (en) | A kind of ionic liquid/polymer electrolyte film and preparation method thereof | |
| Kanbara et al. | Preparation and properties of poly (quinolinediyl) s and poly (isoquinoline-1, 4-diyl) with new π-conjugation systems | |
| CN101392060B (en) | Quaternized polybenzimidazoles and preparation method thereof | |
| Rosi et al. | Hydrogel-polymer electrolytes based on polyvinyl alcohol and hydroxyethylcellulose for supercapacitor applications | |
| CN107174956B (en) | The preparation method of perfluoroethylene-propylene hollow-fibre membrane with finishing coat | |
| CN103456508B (en) | Method for manufacturing graphene composite electrode | |
| CN106053582A (en) | Polyaniline based mercury ion electrode with high sensitivity and preparation method thereof | |
| CN110054792B (en) | SBS-based anion exchange membrane and preparation method thereof | |
| CN104311857A (en) | Preparation method for double quaternary ammonium side long chain anion-exchange membrane | |
| Mateos et al. | Comprehensive study of poly (2, 3, 5, 6-tetrafluoroaniline): from electrosynthesis to heterojunctions and ammonia sensing | |
| CN106147197A (en) | A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof | |
| Liu et al. | Preparation of PAA‐g‐PEG/PANI polymer gel electrolyte and its application in quasi solid state dye‐sensitized solar cells | |
| CN102249733A (en) | Sulfur-alkene click chemistry-based method for preparing stimulation responsive polyether amine macromolecular brush | |
| CN107658478A (en) | A kind of all-vanadium flow battery barrier film and preparation method thereof | |
| CN105806916A (en) | High-sensitivity cadmium ion electrode based on polypyrrole and preparation method thereof | |
| Song et al. | Imidazolium-functionalized anion exchange polymer containing fluorine group for fuel cell application | |
| CN111063548A (en) | Three-dimensional silicon structure/polyaniline-based composite electrode material and preparation method thereof | |
| CN110676072A (en) | Electrochemical energy device and preparation method thereof | |
| CN106018525A (en) | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof | |
| Baicea et al. | Composite membranes with poly (ether ether ketone) as support and polyaniline like structure, with potential applications in fuel cells | |
| CN105136884B (en) | Diaphragm type moisture sensor based on carbon nano-tube/poly vinylpyrrolidone | |
| WO2012074368A1 (en) | Phosphate sensor | |
| CN109243835A (en) | A kind of poly- 3,4- ethene dioxythiophene mesh nanometer film PEDOT-PD and the preparation method and application thereof | |
| CN107887181A (en) | A kind of preparation method of cotton base carbon fibre flexible electrode | |
| CN100398587C (en) | Wave absorption material containing polyaniline, manufacturing method and equipment |
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 | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20190726 |