CN1601268A - Electronic conducting polymer membrane electrode for detecting dihydroxy-benzene and its prepn method - Google Patents
Electronic conducting polymer membrane electrode for detecting dihydroxy-benzene and its prepn method Download PDFInfo
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- CN1601268A CN1601268A CN 200410087823 CN200410087823A CN1601268A CN 1601268 A CN1601268 A CN 1601268A CN 200410087823 CN200410087823 CN 200410087823 CN 200410087823 A CN200410087823 A CN 200410087823A CN 1601268 A CN1601268 A CN 1601268A
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Abstract
The invention relates to an electronic conductive polymer film electrode used for detecting paradioxybenzone and its preparation method. Said invention is characterized by adopting macromolecular function acid to make doping so as to raise electrochemical stability of polymer film and catalytic power of polymer for catalyzing paradioxybenzene. Said polymer film electrode includes indifferent electrode base body and conductive polymer film, said conductive polymer film is poly-o-toluidine in whith toluene-p-sulfonic acid is doped, and the attachment quantity of polymer on the base body electrode surface is 0.3-1.0 mg.-sq.cm. Said invention also provides its preparation method and concrete steps, its once operation can prepare several medified electrodes.
Description
Technical field
The present invention relates to a kind of conducting polymer membrane electrode, especially a kind of electronic conductive polymer membrane electrode that detects at the water pollutant p-dihydroxy-benzene as electrochemical sensor and preparation method thereof.
Background technology
Chemically modified electrode (Chemical modified electrode, CME) be on the conductive electrode surface, chemical group with certain function by physics or chemical method attached to electrode surface, give electrode certain specific character, highly selective carries out desired reaction.It is big that the conductive polymer membrane chemically modified electrode has an electrochemical response signal with respect to the unimolecular layer chemically modified electrode, easily observation, bigger chemistry and electrochemical stability are arranged, be difficult for running off stronger anti-interference and antitoxin harmful ability, electrode favorable reproducibility, characteristics such as long service life, particularly conductive polymer membrane have electroactive, can in oxidation-reduction process, modulate effectively its conductive state and the insulation attitude, have quite important and potential widely using value.New functional electrode in order to obtain to be scheduled to carries out desired reaction, and people are devoted to the polymer film modified electrode that research and design contains various functional groups, as polypyrrole (PPy), polythiophene (PTh), polyaniline (PAn) and derivant thereof etc.This polymer film modified electrode combines galvanochemistry and organic, biological, macromolecule, realized the electrode function design of people's serious hope for many years, have good characteristics such as electro-catalysis, selective permeation, selective enrichment, obtained many significative results at aspects such as electro-catalysis, electroanalysis.
Phenol is main water quality pollutant, and it is the electrochemical research topic of current environment that the monitoring of aldehydes matter and galvanochemistry are removed, and is an important indicator in the environmental analysis.P-dihydroxy-benzene, catechol, three kinds of isomeride physicochemical properties of resorcinol are similar, usually coexistence again, conventional analytical approach such as spectrophotometer method can not directly be measured each component, people have been developed chromatography, fluorescence method etc. gradually (referring to document: Chen Yuluan, Deng, analysis and testing technology and instrument, 1995,1 (4): 21-25) detect, but also all cut both ways.The polyphenol substance detection that develops into of conductive polymer electrodes decorative material provides new development opportunity.With polymkeric substance during as the electrode film decorative material, according to polymkeric substance catalysis p-H
2The current potential of Q oxidation comes the control electrode current potential, can reflect well by detection oxidation peak current density to be detected the substrate concentration size.Fu Yi etc. (referring to document: Fu Yi, etc., analytical test journal, 1998,17 (5): 43-46) reported the electrocatalysis characteristic of polyaniline film modified electrode to polyphenolic substance.Ten thousand strong grades (referring to document: Wan Benqiang, etc., chemical research and application, 1995,7 (2): research 125-130) shows that also polypyrrole has electrocatalysis characteristic to p-dihydroxy-benzene and catechol.
Bibliographical information adopts polyaniline as electrode catalytic materials mostly, but there is its practical application of some problems affect in polyaniline material self.(1) the strong rigidity of PAn macromolecular chain skeleton of aromatic ring structure and hydrogen bond action make interchain produce strong interaction, and the PAn of common protonic acid doping is dissolved in any solvent hardly, and dissolubility and rheological property all are unfavorable for machine-shaping; (2) though inferior doping makes PAn can obtain some excellent properties, but the galvanochemistry of polymkeric substance and poor chemical stability are (referring to document: R.Mazeikiene, et al, European Polymer Journal, 2002,38:1947-1952), and stability the application in electrochemical sensor seems extremely important for electrode modified material.Evelyn Buttner etc. are (referring to document: Evelyn Buttne, et al, Journal of Electro analytical Chemistry, 2001, as the catalysis material of hydroquinone oxidation the polymer degradation phenomenon has appearred with polyaniline film 508:150-155).Therefore, how to utilize effective synthesis process, the preparation good stability, the PAn that has advantageous properties such as good solubility and high conductivity simultaneously becomes problem demanding prompt solution.
On polymer molecular chain, introduce ring substituents, utilize substituent steric effect, increase the strand spacing, reduce the coplanarity of strand, improve solubility property, but the partially conductive of while possibility sacrificial polymer.In substituting group modification PAn research, more employing alkyl, alkoxy, sulfonic ortho position or a position replace the PAn derivant, as Roy etc. (referring to document: Roy BC, et al, Synthetic Metals, 1999,100:233-236) adopt sulfonic group modified PAn, synthesized water miscible PAn derivant.In addition, owing to have a lot of imine groups on the PAn molecular backbone, utilize the reaction capacity of imido grpup, the employing functional acid mixes, reduce the energy level difference of conducting polymer electronic transition, improve its electric conductivity, but protonic acid doping makes simultaneously the solubility property of polymkeric substance reduce greatly.
Summary of the invention
Purpose of the present invention aims to provide the big molecular function acid of a kind of employing and mixes, improve the electrochemical stability of polymer film, improve polymkeric substance the catalytic performance of p-dihydroxy-benzene is used for electronic conductive polymer membrane electrode that p-dihydroxy-benzene detects and preparation method thereof.
Electronic conductive polymer membrane electrode of the present invention comprises inert electrode matrix and conductive polymer membrane, conductive polymer membrane is poly-ortho-aminotoluene (POT) polymkeric substance of p-toluenesulfonic acid (TSA) doping, and the adhesion amount of base electrode surface aggregate thing is 0.3～1.0mgcm
-2
Said inert electrode matrix is platinum disk electrode or glass carbon disk electrode.
The electronic conductive polymer membrane electrode preparation method is as follows:
1) p-toluenesulfonic acid (TSA) mixes synthesizing of poly-ortho-aminotoluene (POT): the molar concentration rate by toluenesulfonic acid/ortho-aminotoluene is 15～7, in reaction vessel, add 1.0mol/L TSA aqueous solution, ice bath, logical nitrogen deoxygenation, treat that temperature stabilization is in 2～3 ℃, drip the ortho-aminotoluene monomer of 0.07～0.14mol/L, add saturated CoSO
4Solution is as catalyzer; Ammonium persulfate (APS) is dissolved in 1.0mol/L TSA solution, the consumption of ammonium persulfate is 0.5～2 to decide by the molar concentration rate of ammonium persulfate/ortho-aminotoluene, splashes in the reaction vessel, continue reaction 6～15h after, reactant liquor places 5～8 ℃ of refrigerators to leave standstill, the suction filtration reactant liquor divides to filtrate with the deionized water wash solid to be neutral, washs with ethanol again, colourless to filtrate: room temperature～60 ℃ following vacuum drying, get TSA doped P OT, or claim doping attitude POT (TSA) polymkeric substance, be green.
2) drop-coating prepares polymer film modified electrode: doping attitude POT (TSA) polymkeric substance is dissolved in N, in the dinethylformamide (DMF), be made into the solution of 1.0～10.0mg/mL, get polymer solution and be coated on electrode surface, promptly get polymer film modified electrode after the oven dry, the adhesion amount of electrode surface polymkeric substance is 0.3～1.0mgcm
-2
The present invention has synthesized a kind of TSA doped P OT, and be the film modified electrode of feedstock production with doping attitude POT (TSA), as the electrochemical sensor that detects p-dihydroxy-benzene in the aqueous medium, have following advantage: (1) adopts methyl substituted in conjunction with having more anionic p-toluenesulfonic acid (TSA) to be carried out doping vario-property to POT, overcome simple ring and replaced the drawback that reduces conducting polymer, and improved the electrochemical stability of polymkeric substance to a great extent; (2) TSA mixes and has improved the active potential range of polymkeric substance, makes that the catalytic active center on the film increases, and improves catalytic performance, at p-H
2In the detection of Q/Q, concentration change there is response sensitivity preferably; (3) chemical method synthetic polymer has been avoided problems such as the general over oxidation that adopts the polymkeric substance that electrochemical polymerization method causes in the document, crosslinked, degraded, and the productive rate height, and cost is low; (4) adopt synchronous doping method, promptly finish doping in building-up process, with respect to the back doping method, not only technology is simple, and effectively doping rate height; (5) drop-coating prepares polymer film modified electrode, can a plurality of modified electrodes of disposable preparation, not only technology is simple, and carry out when helping detecting performance relatively, debugging.
Description of drawings
Fig. 1 is variable concentrations p-H on the film modified electrode of POT in the acid medium (TSA)
2CV spectrogram (sweep velocity: the 50mV/s, [p-H of Q solution
2Q] (mol/L): a=0, b=0.01, c=0.03, d=0.05).In Fig. 1, horizontal ordinate is E/VvsSCE, and ordinate is j/mAcm
-2
Fig. 2 is the film modified electrode detection p-H of POT (TSA)
2J during Q
Pa～[p-H
2Q] relation working curve diagram.In Fig. 2, horizontal ordinate is [p-H
2Q]/molL
-1, ordinate is jpa/mAcm
-2
Embodiment
Embodiment 1:
In the 250mL three-necked bottle, add 100mL 1.0mol/L TSA aqueous solution, ice bath, logical nitrogen deoxygenation is treated temperature stabilization about 2～3 ℃, drips the 2.14g ortho-aminotoluene, [M]=0.01mol/L stirs, and adds 2 saturated CoSO
4Solution is as catalyzer.Ammonium persulfate (APS) is dissolved in 60mL 1.0mol/L TSA solution, and [APS]/[M]=0.01 slowly splashes in the three-necked bottle, and about 2.0h drips off.After continuing reaction 10h, reactant liquor places 5 ℃ of refrigerators to leave standstill 36h; Then with gained reactant liquor suction filtration, divide admittedly to filtrate with deionized water wash to be neutral, with the ethanol washing for several times, colourless again to filtrate; 60 ℃ of following vacuum dryings get green-doped attitude POT (TSA).
POT (TSA) is mixed with the DMF solution of 3.0mg/mL, with miniature vortex mixed instrument hydrotropy; Get a certain amount of polymer solution and be coated on the platinum disk electrode surface, place oven dry 12min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 0.5mgcm
-2
In single compartment electrolytic cell, as working electrode, the platinized platinum electrode is an auxiliary electrode with polymer film modified electrode, and saturated calomel electrode is a contrast electrode.Experiment is carried out on CHI660 galvanochemistry comprehensive tester, and its attached computer software can supply collection of experiment data and processing.Containing p-H
2In the medium of Q, cyclic voltammetry scan is carried out in potentiostat control between-0.2～0.8V, and the film modified electrode of POT (TSA) oxidation peak occurs near the 0.48V current potential, along with p-H
2The increase of Q concentration, the oxidation peak current (see figure 1) that raises gradually, this phenomenon is p-H
2The sensor that Q detects; Fig. 2 is POT (TSA)) modified electrode detects p-H in the medium
2The working curve of Q concentration, oxidation peak current is with p-H
2The increase of Q concentration and raising, and embody good linear relationship, be p-H in the medium
2Q concentration the condition that provides accurately is provided.Therefore, by detecting near the oxidation peak current density size of 0.48V on POT (TSA) modified electrode, can learn p-H in the medium according to working curve
2The content of Q.
Embodiment 2:
In the 250mL three-necked bottle, add 140mL 1.0mol/L TSA aqueous solution, ice bath, logical nitrogen deoxygenation is treated temperature stabilization about 2～3 ℃, drips the 1.5g ortho-aminotoluene, [M]=0.07mol/L stirs, and adds 3 saturated CoSO
4Solution is as catalyzer.APS is dissolved in 10mL 1.0mol/LTSA solution, and [APS]/[M]=0.5 slowly splashes in the three-necked bottle, and about 1.5h drips off.After continuing reaction 6h, reactant liquor places 6 ℃ of refrigerators to leave standstill 48h; Then with gained reactant liquor suction filtration, divide admittedly to filtrate with deionized water wash to be neutral, with the ethanol washing for several times, colourless again to filtrate; Room temperature ℃ following vacuum drying gets green-doped attitude POT (TSA).
POT (TSA) is mixed with the DMF solution of 3.0mg/mL, with miniature vortex mixed instrument hydrotropy; Get a certain amount of polymer solution and be coated on the platinum disk electrode surface, place oven dry 15min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 0.3mgcm
-2
Embodiment 3:
In the 250mL three-necked bottle, add 200mL 1.0mol/L TSA aqueous solution, ice bath, logical nitrogen deoxygenation is treated temperature stabilization about 2～3 ℃, drips the 3.0g ortho-aminotoluene, [M]=0.14mol/L stirs, and adds 3 saturated CoSO
4Solution is as catalyzer.APS is dissolved in 100mL 1.0mol/L TSA solution, and [APS]/[M]=2 slowly splash in the three-necked bottle, and about 3.0h drips off.After continuing reaction 15h, reactant liquor places 8 ℃ of refrigerators to leave standstill 24h; Then with gained reactant liquor suction filtration, divide admittedly to filtrate with deionized water wash to be neutral, with the ethanol washing for several times, colourless again to filtrate; 40 ℃ of following vacuum dryings get green-doped attitude POT (TSA).
POT (TSA) is mixed with the DMF solution of 3.0mg/mL, with miniature vortex mixed instrument hydrotropy; Get a certain amount of polymer solution and be coated on glass carbon disk electrode surface, place oven dry 10min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 1.0mgcm
-2
Claims (3)
1, a kind of electronic conductive polymer membrane electrode that is used for the p-dihydroxy-benzene detection, it is characterized in that comprising inert electrode matrix and conductive polymer membrane, conductive polymer membrane is the poly-ortho-aminotoluene polymkeric substance of p-toluenesulfonic acid doping, and the adhesion amount of base electrode surface aggregate thing is 0.3～1.0mgcm
-2
2, a kind of electronic conductive polymer membrane electrode that p-dihydroxy-benzene detects that is used for as claimed in claim 1 is characterized in that said inert electrode matrix is platinum electrode or glass-carbon electrode.
3. the described a kind of electronic conductive polymer membrane electrode preparation method that p-dihydroxy-benzene detects that is used for of claim 1 is characterized in that the steps include:
1) p-toluenesulfonic acid mixes synthesizing of poly-ortho-aminotoluene: the molar concentration rate by toluenesulfonic acid/ortho-aminotoluene is 15～7, in container, add 1.0mol/L TSA aqueous solution, ice bath, logical nitrogen deoxygenation, treat that temperature stabilization is in 2～3 ℃, drip the ortho-aminotoluene of 0.07～0.14mol/L, add saturated CoSO
4Solution is as catalyzer; Ammonium persulfate is dissolved in 1.0mol/LTSA solution, the consumption of ammonium persulfate is 0.5～2 by the molar concentration rate of ammonium persulfate/ortho-aminotoluene, splash in the container, after continuing reaction 6～15h, reactant liquor leaves standstill under 5～8 ℃, the suction filtration reactant liquor divides to filtrate with the deionized water wash solid to be neutral, washs to filtrate colourless with ethanol again; Room temperature～60 ℃ following vacuum drying gets the poly-ortho-aminotoluene that p-toluenesulfonic acid mixes;
2) preparation polymer film modified electrode: doping attitude POT (TSA) polymkeric substance is dissolved among the DMF, be made into the solution of 1.0～10.0mg/mL, get polymer solution and be coated on electrode surface, promptly get polymer film modified electrode after the oven dry, the adhesion amount of electrode surface polymkeric substance is 0.3～1.0mgcm
-2
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| CN101581694B (en) * | 2009-06-20 | 2012-05-09 | 西北师范大学 | Electrochemical detection method for quinhydrone |
| CN101532983B (en) * | 2009-04-11 | 2012-07-25 | 桂林工学院 | Preparation method of bis-Schiff base chromium (III) ion selective electrode and use thereof |
| CN101532984B (en) * | 2009-04-11 | 2012-07-25 | 桂林工学院 | Preparation method of ion selective electrode capable of measuring trace chromium (III) |
| CN104034774A (en) * | 2014-06-26 | 2014-09-10 | 西安工程大学 | Polymerized reactive brilliant orange K-7R membrane electrode, as well as preparation method and application method thereof |
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2004
- 2004-10-22 CN CN 200410087823 patent/CN1601268A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532983B (en) * | 2009-04-11 | 2012-07-25 | 桂林工学院 | Preparation method of bis-Schiff base chromium (III) ion selective electrode and use thereof |
| CN101532984B (en) * | 2009-04-11 | 2012-07-25 | 桂林工学院 | Preparation method of ion selective electrode capable of measuring trace chromium (III) |
| CN101581694B (en) * | 2009-06-20 | 2012-05-09 | 西北师范大学 | Electrochemical detection method for quinhydrone |
| CN104034774A (en) * | 2014-06-26 | 2014-09-10 | 西安工程大学 | Polymerized reactive brilliant orange K-7R membrane electrode, as well as preparation method and application method thereof |
| CN104237346A (en) * | 2014-10-09 | 2014-12-24 | 无锡百灵传感技术有限公司 | Electrochemical sensor for detecting pH value of purified water online |
| CN104237346B (en) * | 2014-10-09 | 2016-08-24 | 无锡百灵传感技术有限公司 | The electrochemical sensor of on-line checking purified water pH value |
| CN109900780A (en) * | 2019-04-02 | 2019-06-18 | 厦门历思科技服务有限公司 | The online pretreating device of hair sample sample introduction |
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