CN104962945A - Electrochemical synthesis method of polyaniline with sea urchin-shaped nanostructures - Google Patents
Electrochemical synthesis method of polyaniline with sea urchin-shaped nanostructures Download PDFInfo
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- CN104962945A CN104962945A CN201510258303.8A CN201510258303A CN104962945A CN 104962945 A CN104962945 A CN 104962945A CN 201510258303 A CN201510258303 A CN 201510258303A CN 104962945 A CN104962945 A CN 104962945A
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- sea urchin
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Abstract
The invention relates to an electrochemical synthesis method of polyaniline with sea urchin-shaped nanostructures. The electrochemical synthesis method comprises following steps: (1) aniline monomer and an acid-doped electrolyte solution are prepared; (2) a three-electrode system is adopted, and electrochemical polymerization of aniline is realized via cyclic voltammetry; and (3) obtained polyaniline-modified electrodes are subjected to immersion cleaning with deionized water, and an obtained product is dried in a vacuum drying oven so as to obtain a blackish green polyaniline product with sea urchin-shaped nanostructures. Advantages of the electrochemical synthesis method are that: synthesis process is simple, no impurity is introduced, synthesis process can be completed at normal temperature, no special low temperature environment is required, and the structure of obtained polyaniline is controllable. Application prospect of polyaniline with sea urchin-shaped nanostructures in the fields such as sensor, capacitor, corrosion resistance, and pollution resistance is promising.
Description
Technical field
The invention belongs to polyaniline synthetic technology and nanostructure synthesis field, be specifically related to a kind of electrochemical method for synthesizing of micrometer/nanometer structure polyaniline of sea urchin shape.
Background technology
Later 1970s, the people such as Shirakawa, MacDiarmid, Heeger find that the polyacetylene of doping state has metallic character and electroconductibility, thus open the gate of conducting polymer.Polyaniline is as a kind of conducting polymer, because it exists multiple oxidation state, there is electricity and optical activity, and aniline monomer is with low cost, the features such as oxidation/reduction reversibility and chemical stability, are paid close attention to widely in rechargable power supplies, sensor, magnetic shielding, electrochemical capacitor, the field such as anticorrosion and antifouling and are applied.
In recent years, the polyaniline of nanostructure enjoys favor because it shows excellent character in electricity, optics etc. in scientific circles, emerges in an endless stream especially to the research of its synthetic method and application.Polyaniline nano structure comprises nano wire, nanometer rod, nanotube and nanofiber etc.The synthetic method of current micrometer/nanometer structure polyaniline comprises template, self-assembly method, electrochemical process, sonochemistry polymerization, interfacial polymerization, electrostatic spinning etc.Wherein electrochemical method comprises cyclic voltammetry, potentiostatic method, galvanostatic method etc.Qin Zongyi etc. [CN 103408754A] adopt a kind of solution method of uniqueness to successfully synthesize polyaniline nano fiber.The method without the need to using template, and reaction in aqueous phase, carry out thus product postprocessing simple, can be used in large-scale mass production.Wang Jixiao etc. [CN 101139440A] have adopted single stage method to prepare to have the polyaniline of nanometer sheet structure, and its preparation process is simple, and the purity of polyaniline can up to 100%.Kan Jinqing etc. adopt electrochemical method, have prepared polyaniline nano fiber [CN 1958854A], have had the feature of uniform particle sizes, queueing discipline.Pan Mu etc. [CN 103255433A] adopt two electrode systems, the electrochemical method for synthesizing of Fast back-projection algorithm electrically conductive polyaniline under big current, and obtaining in nano bar-shape structure, diameter is the polyaniline of 100-350nm.Although there has been the synthetic method of the polyaniline of a lot of nanostructure at present, the synthetic method seeking novel nano structure polyaniline has still had great importance.
Summary of the invention
Object of the present invention solves the deficiencies in the prior art, provides a kind of electrochemical method for synthesizing of sea urchin shape micrometer/nanometer structure polyaniline of simple possible.
The electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure adopts cyclic voltammetry, in three-electrode system, electrochemical polymerization aniline in the mixed electrolytic solution that aniline and proton dopant acid form, be polymerized the product terminating rear working electrode is modified and be polyaniline, its pattern is sea urchin shape nanostructure.
The concrete steps of the electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure are as follows:
(1) the chromatographic grade polyaniline being more than or equal to 99.98% being joined concentration is 0.8 ~ 1 molL
-1proton dopant acid solution in, stir, the concentration of polyaniline controls at 0.1 ~ 0.45molL
-1, the mixing solutions obtained is as electrolyte solution, stand-by;
(2) mixing solutions is injected in electrolyzer as electrolyte solution, take saturated calomel electrode as reference electrode, with the platinum filament of diameter to be the platinum disk electrode of 2 mm or diameter be 1 mm for electrode, take diameter as the platinum filament of 1 mm be working electrode, the length of working electrode is 6 ~ 8 cm, the length being immersed in the platinum filament in electrolytic solution is 1 ~ 3 cm, magnetic agitation, and magneton rotating speed is 120 ~ 150 rmin
-1;
(3) adopt cyclic voltammetry electrochemical polymerization aniline at 10 ~ 30 DEG C, the optimum configurations of cyclic voltammetry is: voltage range is-0.1 ~ 1 V vs. SCE, and scanning speed is 5 ~ 20mv s
-1, scanning times is 2 ~ 25 times;
(4) after being polymerized, the platinum filament being modified with polyaniline being taken out from electrolytic solution, embathes with deionized water, the proton dopant acid of removing polyaniline surface attachment;
(5) will platinum filament vacuum-drying 40 ~ 50h in the vacuum drying oven of 30 ~ 35 DEG C of polyaniline be modified with, the polyaniline of sea urchin shape nanostructure can be obtained.
Described proton dopant acid is hydrochloric acid, phosphoric acid or perchloric acid.The polyaniline of described sea urchin shape nanostructure is the polyaniline of blackish green sea urchin shape nanostructure.
The beneficial effect that the present invention compared with prior art has:
(1) electrolytic solution composition is simple.Method of the present invention electrolytic solution used is the mixing solutions of aniline and mineral acid, and the product therefore obtained is the polyaniline of acid doping, and containing other impurity as initiator, oxygenant or tensio-active agent.
(2) polymerizing condition is simple.The present invention adopts cyclic voltammetry electrochemical polymerization aniline, and this polyreaction at room temperature can be carried out, and does not need the environment providing low temperature.
(3) product postprocessing is simple.As described in (1), product that polyaniline obtains is directly the polyaniline of acid doping to adopt method of the present invention to prepare, and therefore product postprocessing process only needs vacuum-drying and eliminates the complicated processes removing impurity and purification.
(4) structure-controllable of polyaniline.Under experiment condition of the present invention, the polyaniline obtained is the blackish green polyaniline of the sea urchin shape nanostructure of acid doping.
The polyaniline of the sea urchin shape nanostructure prepared by the present invention is expected to obtain wide application prospect in fields such as sensor, electrical condenser, anti-corrosion of metal, bioantifoulings.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture (SEM) of the sea urchin shape micrometer/nanometer structure polyaniline that the present invention obtains.
Embodiment
The electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure adopts cyclic voltammetry, in three-electrode system, electrochemical polymerization aniline in the mixed electrolytic solution that aniline and proton dopant acid form, be polymerized the product terminating rear working electrode is modified and be polyaniline, its pattern is sea urchin shape nanostructure.
embodiment 1:
In the present embodiment, the concrete steps of the electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure are as follows:
(1) the chromatographic grade polyaniline being more than or equal to 99.98% being joined concentration is 1 molL
-1hydrochloric acid soln in, stir, the concentration of polyaniline controls at 0.1molL
-1, the mixing solutions obtained is as electrolyte solution, stand-by;
(2) mixing solutions is injected in electrolyzer as electrolyte solution, take saturated calomel electrode as reference electrode, the platinum disk electrode being 2 mm with diameter is to electrode, take diameter as the platinum filament of 1 mm be working electrode, the length of working electrode is 6 cm, the length being immersed in the platinum filament in electrolytic solution is 1 cm, magnetic agitation, and magneton rotating speed is 120 rmin
-1;
(3) adopt cyclic voltammetry electrochemical polymerization aniline at 10 DEG C, the optimum configurations of cyclic voltammetry is: voltage range is-0.1 ~ 1 V vs. SCE, and scanning speed is 5 mv s
-1, scanning times is 25 times;
(4) after being polymerized, the platinum filament being modified with polyaniline being taken out from electrolytic solution, embathes with deionized water, the hydrochloric acid of removing polyaniline surface attachment;
(5) will platinum filament vacuum-drying 40 h in the vacuum drying oven of 30 DEG C of polyaniline be modified with, the polyaniline of sea urchin shape nanostructure can be obtained.
embodiment 2:
In the present embodiment, the concrete steps of the electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure are as follows:
(1) the chromatographic grade polyaniline being more than or equal to 99.98% being joined concentration is 0.8 molL
-1phosphoric acid solution in, stir, the concentration of polyaniline controls at 0.45molL
-1, the mixing solutions obtained is as electrolyte solution, stand-by;
(2) mixing solutions is injected in electrolyzer as electrolyte solution, take saturated calomel electrode as reference electrode, the platinum filament being 1 mm with diameter is to electrode, take diameter as the platinum filament of 1 mm be working electrode, the length of working electrode is 8 cm, the length being immersed in the platinum filament in electrolytic solution is 3 cm, magnetic agitation, and magneton rotating speed is 150 rmin
-1;
(3) adopt cyclic voltammetry electrochemical polymerization aniline at 30 DEG C, the optimum configurations of cyclic voltammetry is: voltage range is-0.1 ~ 1 V vs. SCE, and scanning speed is 20mv s
-1, scanning times is 2 times;
(4) after being polymerized, the platinum filament being modified with polyaniline being taken out from electrolytic solution, embathes with deionized water, the phosphoric acid of removing polyaniline surface attachment;
(5) will platinum filament vacuum-drying 50h in the vacuum drying oven of 35 DEG C of polyaniline be modified with, the polyaniline of sea urchin shape nanostructure can be obtained.
embodiment 3:
In the present embodiment, the concrete steps of the electrochemical method for synthesizing of the polyaniline of sea urchin shape nanostructure are as follows:
(1) the chromatographic grade polyaniline being more than or equal to 99.98% being joined concentration is 1 molL
-1perchloric acid solution in, stir, the concentration of polyaniline controls at 0.15molL
-1, the mixing solutions obtained is as electrolyte solution, stand-by;
(2) mixing solutions is injected in electrolyzer as electrolyte solution, take saturated calomel electrode as reference electrode, the platinum filament being 1 mm with diameter is to electrode, take diameter as the platinum filament of 1 mm be working electrode, the length of working electrode is 7 cm, the length being immersed in the platinum filament in electrolytic solution is 2 cm, magnetic agitation, and magneton rotating speed is 130 rmin
-1;
(3) adopt cyclic voltammetry electrochemical polymerization aniline at 30 DEG C, the optimum configurations of cyclic voltammetry is: voltage range is-0.1 ~ 1 V vs. SCE, and scanning speed is 5 mv s
-1, scanning times is 20 times;
(4) after being polymerized, the platinum filament being modified with polyaniline being taken out from electrolytic solution, embathes with deionized water, the perchloric acid of removing polyaniline surface attachment;
(5) will platinum filament vacuum-drying 48 h in the vacuum drying oven of 30 DEG C of polyaniline be modified with, the polyaniline of sea urchin shape nanostructure can be obtained.
The polyaniline of the described sea urchin shape nanostructure obtained is the polyaniline of blackish green sea urchin shape nanostructure.
Claims (4)
1. the electrochemical method for synthesizing of the polyaniline of a sea urchin shape nanostructure, it is characterized in that: adopt cyclic voltammetry, in three-electrode system, electrochemical polymerization aniline in the mixed electrolytic solution that aniline and proton dopant acid form, be polymerized the product terminating rear working electrode is modified and be polyaniline, its pattern is sea urchin shape nanostructure.
2. method according to claim 1, is characterized in that the concrete steps of method are as follows:
(1) the chromatographic grade polyaniline being more than or equal to 99.98% being joined concentration is 0.8 ~ 1 molL
-1proton dopant acid solution in, stir, the concentration of polyaniline controls at 0.1 ~ 0.45molL
-1, the mixing solutions obtained is as electrolyte solution, stand-by;
(2) mixing solutions is injected in electrolyzer as electrolyte solution, take saturated calomel electrode as reference electrode, with the platinum filament of diameter to be the platinum disk electrode of 2 mm or diameter be 1 mm for electrode, take diameter as the platinum filament of 1 mm be working electrode, the length of working electrode is 6 ~ 8 cm, the length being immersed in the platinum filament in electrolytic solution is 1 ~ 3 cm, magnetic agitation, and magneton rotating speed is 120 ~ 150 rmin
-1;
(3) adopt cyclic voltammetry electrochemical polymerization aniline at 10 ~ 30 DEG C, the optimum configurations of cyclic voltammetry is: voltage range is-0.1 ~ 1 V vs. SCE, and scanning speed is 5 ~ 20mv s
-1, scanning times is 2 ~ 25 times;
(4) after being polymerized, the platinum filament being modified with polyaniline being taken out from electrolytic solution, embathes with deionized water, the proton dopant acid of removing polyaniline surface attachment;
(5) will platinum filament vacuum-drying 40 ~ 50h in the vacuum drying oven of 30 ~ 35 DEG C of polyaniline be modified with, the polyaniline of sea urchin shape nanostructure can be obtained.
3. method according to claim 2, is characterized in that described proton dopant acid is hydrochloric acid, phosphoric acid or perchloric acid.
4. method according to claim 1, is characterized in that the polyaniline of described sea urchin shape nanostructure is the polyaniline of blackish green sea urchin shape nanostructure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461920A (en) * | 2015-12-16 | 2016-04-06 | 华南师范大学 | Method for synthesizing sea-urchin-shaped gold nanoparticles and spherical polyaniline through one-pot method and applications |
| CN111272842A (en) * | 2020-02-25 | 2020-06-12 | 衡阳师范学院 | Polyaniline modified electrode for quantitatively detecting estrone and preparation method and application thereof |
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| JPH03173787A (en) * | 1989-11-30 | 1991-07-29 | Central Glass Co Ltd | Production of polyaniline |
| US20050153130A1 (en) * | 2004-01-13 | 2005-07-14 | Long Jeffrey W. | Carbon nanoarchitectures with ultrathin, conformal polymer coatings for electrochemical capacitors |
| CN102505130A (en) * | 2011-12-01 | 2012-06-20 | 昆明理工大学 | Polyaniline-coated Al-based Pb-WC composite anode and preparation method thereof |
| CN102516764A (en) * | 2011-11-17 | 2012-06-27 | 华东理工大学 | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof |
| CN103063722A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid calcium ion electrode based on conductive polyaniline and preparing method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03173787A (en) * | 1989-11-30 | 1991-07-29 | Central Glass Co Ltd | Production of polyaniline |
| US20050153130A1 (en) * | 2004-01-13 | 2005-07-14 | Long Jeffrey W. | Carbon nanoarchitectures with ultrathin, conformal polymer coatings for electrochemical capacitors |
| CN102516764A (en) * | 2011-11-17 | 2012-06-27 | 华东理工大学 | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof |
| CN102505130A (en) * | 2011-12-01 | 2012-06-20 | 昆明理工大学 | Polyaniline-coated Al-based Pb-WC composite anode and preparation method thereof |
| CN103063722A (en) * | 2012-12-13 | 2013-04-24 | 浙江大学 | Solid calcium ion electrode based on conductive polyaniline and preparing method thereof |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461920A (en) * | 2015-12-16 | 2016-04-06 | 华南师范大学 | Method for synthesizing sea-urchin-shaped gold nanoparticles and spherical polyaniline through one-pot method and applications |
| CN105461920B (en) * | 2015-12-16 | 2018-02-23 | 华南师范大学 | Method and the application of one pot process sea urchin shape golden nanometer particle and spherical polyaniline |
| CN111272842A (en) * | 2020-02-25 | 2020-06-12 | 衡阳师范学院 | Polyaniline modified electrode for quantitatively detecting estrone and preparation method and application thereof |
| CN111272842B (en) * | 2020-02-25 | 2022-09-30 | 衡阳师范学院 | Polyaniline modified electrode capable of quantitatively detecting estrone and preparation method and application thereof |
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